Document q6v2o7Gvg4vawynZxz3pgmYM
I
April 1, 1993
Concannon & Jaeger
General Court Reporters
705 Olive Street, Suite 604 St. Louis, Missouri 63101
1 (314) 421-1000
WATER PCB-SD0000056441
COMPUTER AIDED TRAMSCRIPTION
1 IK THE UNITED STATES DISTRICT COURT
FOR THE DISTRICT OP NEVADA 2
3 NEVADA POWERCOMPANY,
)
) 4 Plaintiff, )
)
5 "VS*"
)
)
6)
MONSANTOCOMPANY, et al.,
)
7) Defendants. )
8
CV-S-89-555-LDG (LRL)
9 ..
DISCOVERY DEPOSITION OF WITNESS, to oe used in an
10 action pending in the District Court of the United States,
11 for the District of Nevada, wherein NEVADA POWER COMPANY is
12 Plaintiff, and MONSANTO COMPANY, et al., are the
-
13 Defendants, pursuant to Notice, under the provisions of
14 Rule 26 of the Rules of Civil Procedure, taken on April 1,
15 1993, at the lav; offices of Messrs. Hus eh Eppenberger,
16 100 U. Broadway, St. Louis, Missouri, before Mark D.
17 Concannon, a Notary Public within and for the State of
18 Missouri.
19
APPEARANCES
.
20 The Plaintiff was represented by Attorney Ralph A. Bradley of the law firm of Jones, Jones, Close & Brown,
21 Chartered, 7 00 Bank of America PIas a, 3 00 South Fourth street, Ste. 700, Las Vegas, Nevada 89101, and Richard
22 Hinckley, Vice-President/General Counsel, Nevada Power.
23 The Defendant, Monsanto, was represented by Attorney Bruce A, Feather stone of the lav; firm of Kirkland & Ellis,
24 1999 Broadway, Ste. 4000, Denver, Colorado 70202.
25
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1 A P P E A R A H C E S {scontinuing) 2 The Defendant, Westinghouse, was represented by
Attorney Laurie Beech of the law firm of Weil, Gotshal & r>3 Manges, 767 Fifth Avenue, Mew York, New York 10153. 4 Also present: Lis Gini, paralegal. 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25
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COMPUTER AIDED TRANSCRIPTION
DAVID WOOD,ox iav/ful age, being first duly sworn to tell the truth, the whole truth, and nothing but the truth, deposes and says on behalf of the Plaintiff, as follows;
DIRECT EXAMINATION QUESTIONS BY MR. BRADLEY;
Q. Would you please state your name and spell your last for the record.
A. My name is David Wood, w-o-o-d* Q. Mr. Wood, ray name is Ralph Bradley. We introducod ourselves to one another just a few moments ago? is that true? h. Yes. Q. And you understand that I represent Nevada Power Company in this lav?suit they brought against Monsanto, General Electric, and Westinghouse? is that correct ? A. Yes. Q. if during the course of the deposition I ask a question that you don't understand, will you tell me? A. Yes. Q. And if at any point during the deposition you want to take a break for whatever reason, just let us know and we'll accommodate you. All right? A. Thankyou.
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1
. Q,,
Did you review any documents in preparation
2 for today's deposition?
3 A. Yesterday I did look at one or two documents
4 tnat we produced containing my name that had been trans
5 ferred to you.
6 Q, Do you recall which documents those were?
7 A, No, not in detail.
8 Q. Do you recall the date of them, roughly?
9 ti. They covered part of a period between 1966 and
10 1975-'76.
11 Q - And were they -- The documents that you 7 O.i. of reviewed, were those letters written by you? X -J A. Some of them were written by me and some or
14 them were received by me.
'
15 0. Other than letters written to you or by you,
16 did you review any other materials in preparation for
17 today's deposition?
1 8 A. The package of documents contained certain
IS attachments that were attached to what had been sent to me,
20 q. All right. Other than the letters and the
21 attachments, did you review any documents to prepare for
22 today's deposition?
23 A. I believe not.
2 4 Q, /0* C. before?
Okay. Have you had your deposition taken
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1 A. Yea, I have. 2 Q. When diet you have your deposition taken 3 4 A. My deposition was taken in 1992c and in an 5 earlier period which would probably have been in the perioo 6 of 1986 or '87. 7 q. What case was it in *92 that resulted in your 8 having your deposition taken? 9 A, I don't recollect. 10 Q, Was your depositiontaken here in St, Louis? 11 At Yes, it was. 12 Q. What subject matters were coveredin your 13 deposition? 14 A, My understanding of the use of Aroclor, PCB13 reiated dielectric fluids m electrical equipment. 16 Q, And can you be more specific about what the 17 subject matter of your deposition was in '92? For example, 1 B what particular use of PGB-related dielectric fluids did 19 you discuss in your deposition? 20 A. I really don't recall in 1992 the particular 21 subject matter, or indeed the case in question. 22 Q. Do you remember what legal issue was involved? 23 At in that particular case, no, I don't. 24 Q. Okay. Were you represented by an attorney in 25 1992 when you had your deposition taken?
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1 A 1 <5 S f X WAS. r\* Q. And who was that attorney? 3 A, I don1t recall. 4 Q. Was your doposition transcribed? 5 A. Yes, it was. 6 Q. Did you sign it? 7 A. Yea, 1 did. 8 Q. Do you have acopy of it? 9 A, Do, X don't. 10 Q. Who has a copy? do you know? 11 A. The 1 assume that the Monsanto counsel 12 v?ould have a copy of that. 13 Q. Are you represented by an attorney today? 14 Ye; 15 Q. Mr. Peatherstone? 16 A. Yes. 17 Q. Wnat was the subject matter of the deposition 1 0 you had taken in 1986 or 1987? 19 A. That was a case that involved a transformer 20 fire in San Francisco. 21 Q. Going back to the 1992 deposition, do you 22 recall the names of any of the parties in that lawsuit? 23 A. My mind is a blank on the 1992 deposition. 2 4 Q. Does Stroh Die Casting sound familiar to you? 2 3 A. No.
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1 Q Do you recall the names of any attorneys that & were present duringyour 1992 deposition!'' 3 A. No. 4 Q. Do you know whether the case in which you gave 5 a deposition in 1992 resulted in a trial? 6 A, It didn* t. 7 Q. It didnot result in a trial? C h. Correct. 0 Q. Did it settle? 10 A. I don* t know. Tothe best of rayrecollection, ii the deposition I gave in 1992 did not involve chlorinated 12 biphenyls. 13 Q. All right. What was the nature of the deposi 14 tion you gave in 1986-* 87? 15 A. There had been, ina large building in San 1G Francisco, fume damage to the interior of the building 17 resulting from the involvement in a volt transformer in the 18 street outside the building, and the damage to the interior 15 of the building had resulted in renovation of the interior 20 of the building. The insurance company who had processed 21 the claim for the damage to the interior of the building 22 was seeking to recover certain of their damage from 23 Monsanto and others. 2 4 Q. And did you testify in that deposition about 25 the work you had done at Monsanto related to chlorinated
CONCANNON & JABG3R
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1 2) 1 pis eny is?
2 h, Yes.. I did.
3 Q. i now would like you to give me a summary of
4 your educational history beginning with your first college
S attendance.
6 A. I attended Trinity College Cambridge, in
7 England, and I have a degree in the natural Sciences, and
8 part two. of the Law Tripos.
9 Q. Okay.
10 A. That gave me a Bachelor of Arts in natural
11 Science,
12 The degree system of an expert is different in 13 England to the United States. When I left Cambridge Uni
14 versity I joined Monsanto in Great Britain and have worked
*> r: JL
with Monsanto from that tine to the present.
10 Q. Does the degree you received indicate you
1? received a Bachelor's Degree?
1 8 A. I received a Bachelor's Degree, yes.
IS
q. All right.And in Great Britain is that
the
20 equivalent of some similar degree from American universi
21 ties? & zr> r\ A.
The degree system in Cambridge University says
o r> 4m \J
that X could, in a three-year period, which l spent at
2 4 Cambridge University, gain the equivalent in American terms
2 5 of a BBC in science, and have proceeded through a one-year
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1 lav; coarse which would have exempted me from two years of * chamDors work had I chosen to pursue the law as an active3 legal profession. 4 Q. And you indicated that you studied Natural 5 Sciences,* is that correct? 6 A. That is correct. 7 Q. And when did you attend Trinity College? 8 A. 1957 to *59. 9 Q. Oow old were you when you began college? XO A. Seventeen. 11 Q. As part of your study of natural sciences, aid 12 you study polychlorinated biphenyls? 13 A. No, I die not. 14 Q. You also indicated that you studied part two 15 of the Lav; Tripos? 16 A. That is correct. 17 Q. What is the Law Tripos? 18 A. The Law Tripos is the three-year study of lav;, IS wnich is then followed by another two years of chamber 20 work, which would have equipped me to practice law and be 21 called to the bar in Great Britain. 22 In part two of the Law Tripos, 1 essentially 23 covered the theoretical study of contract law, communal 2 4 property, history of law. Those were the major areas of 25 o w LI
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I Q. linen you began work with Monsantor was that in 2 their Great Britain office? 3 A. Yes, it was. 4 Q. What year did youbegin work for Monsanto? 5 A. 195 3. 6 Q. What job title did youhave when you began 7 work for Monsanto in 195 9? 8 A. Bales trainee. 9 Q. What work did you do as a sales trainee? 10 A. I began to learn about Monsanto, Monsanto* s II line of products, the benefits that those products could X bring to the British industry, and to learn how to sell n those products to British industrial users of the chemicals 14 that Monsanto produced. 15 Q. As a sales trainee, I take it you were receiv 15 ing training from one person or several people? 17 A I was receiving training from many people. 18 Q. And how long were you a sales trainee? 19 A. Approximately one year. 20 q. During the one year you were a sales trainee, 21 did you learn that Monsanto manufactured polychlorinated 22 biphenyls? 23 A. Mo, I did not. 2 4 Q. What work -- Excuse me. What was your next: 25 job title?
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1 A. The neat job title was salesman in the United 2 ivi AQUOut 3 Q. How long were you a salesman in the United 4 Kingdom ior Monsanto? 5 A, Approximately two to three years. o/ Q. Who was your supervisor when you were a sales 7 man at Monsanto? 6 A. Dennis Hope. 9 w 0"P"0? 10 A. Uh-huh II Q. What work aid you do as a salesman ior 12 Monsanto in the Uni tea Kingdom? 13 A. 1 was soiling organic silicates, which were 14 used in the precision casting of toughened metals ior 15 applications such as the rotating blades in jet aviation. 16 Q. During that two-to-three-year period when you 17 were a salesman, did you sell products containing poly18 cnlorinated hiphenyls? 19 A. Mo, I did not. 20 Q. what was your next job title? 21 A. I was a European-wide salesman. 22 G. What was your job title? 23 A. Sales representative. 2 4 Q. And was it sales representative, period, or 23 sales representative ior Europe?
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J1L h. I don't believe we made that distinction.
0 Q. All right. Bat your job responsibilities
3 involved sales throughout Europe?
4 A. At that point, yes, throughout Europe.
5 Q. And what year did you become a sales repre
6 sentative?
7 A. I don't recall.
8 Q. Would it have been in roughly 1962 or *63?
9 A. Given the time I joined Monsanto, it would
10 have been likely to have been in that period.
11 q. How long wore you a sales representative ior
12 ^ i o ns a _ ^t o h
13 A, Essentially through 1966 or `67,
14 Q. Daring the time you wore a sales representa
15 tive, were you involved in the sale or Monsanto products
16 containing polychlorinated biphenyls?
17 A. Yes, I was.
16 Q. what information -- Well, let me ask this:
19 What products were you selling as a sales representative
20 that contained PCBs manufactured by Monsanto?
21 A. I was involved in sales of Aroclor capacitor
22 fluids and Pyroclor transformer fluids.
23 Q. Were you involved in the sale of Pyranol
2 4 transformer fluids, as well?
o r*
4* mJ
A. 1 should explain. That's when I sold
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COHCANNON & JAEGER
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1 pyroclor. In Europe Monsanto sold PCB-containing trans
2 former fluids under a trademark, Pyroclor, They were
8 similar to the fluids which were sold in the United States
4 under various other corporate, such as GE, Pyranol, 5 Kestinghouse -- Pyranol was a trademark of General
6 Electric* Inerteen was a trademark of Westinghouse.
7 Q. During the 19 --* During the time you were a
8 sales representative, did you sell products that contained
9 the equivalent of Aroelor 1242?
10 A* Yea, I did.
11 Q. Under what brand name?
12 A. Pyroclor, probably.
18 g. During the time you were a sales representa
14 tive, how many formulations of Pyroclor were you selling?
1 !i A. Pyroclor was -- There were no more than two
16 formulations that I recall of Pyroclor.
17 Q. V7hat were the formulations that you recall
18 selling while you were a sales representative?
19 A. One was a mixture of a higher chlorinated 20 Aroclor, Aroclor 1260, with trichlorobenzene, with a small 21 addition of tetra phenyl tin as a scavenger.
22 Q. Would you spell that for rue? 23 A. T~c--t-r-a, tetra, phenyl, p~h-e-n-y-l, tin,
24 t-i-n. O4* c
And the other was a mixture of higher
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1 chlorinated biphenyl, with trich1orobenaene with ?PQ as a 2 scavenger. 3 Q. Did the Pyroelors have specific names that you 4 referred to them by? 5 A. Pyroclor. 6 Q. Did the different formulations nave specific 7 names? 8 A. I don* t recall. 9 Q. You had indicatedearlier -- Let meask it 10 this way j Did the first formulation relate to the trade*11 mark of Inerteen or Pyranoi? 12 A. I* m sorry. I* ra not sure I under stand your 13 ouo s 11 o n 14 Q, Did the first formulation resemble Inerteen or 15 Py r and ? 16 A, The first formulation that I mentioned related 17 to Pyranol, the second formulation related more closely to 1 8 Inerteen. 19 Q. VJho within Monsanto, if you know, was 20 responsible for selling PCD products in Europe that were 21 similar but not identical to Pyr&nol? 22 A. Are you asking me, were there other companies 2 3 selling similar materials or who was responsible within 2 4 Monsanto for those products? 25
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1 Mil. FEATHERS TOMB; Well, you1 re obviously 2 excluding hr. Wood, who sold a Pyroclor that was similar to 3 but not identical to PyrancI, 4 THE WITNESS: You're going to have to ask rue 5 the question again, 6 Q. (by Mr* Bradley) I'm interested in knowing 7 who within Monsanto determined that for its European sales 8 it would sell a product that was similar to but not identi 9 cal to Pyranoi, which was sold in the United States. 10 MR. FSATKERSTOt-JE: Object to the norm of the 11 CJL1Q S'C i Oil* 12 Q. (by Mr. Bradley) The way the rules for depo 13 sitions work# when an objection is made, you're still 14 required to answer unless you're instructed not to. So go 15 ahead and answer ray question. 16 A. The formulation of transformer fluids that 17 Monsanto sold in that period in Europe would be proposed by 18 the business management in the United States# and at such 19 time as they nad recommended a formulation to be sold, we 20 would conduct studies in Europe to make sure that material 21 sale was compatible with responsible business practice in 22 comparison to competitive materials sold by French, German 23 and Italian producers of similar materials. 24 Q. Did you ever apeak with anyone within the 25 business group of Monsanto in the United States where they
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COMPUTER AIDED TRANSCRIPTION
1 indicated to you the reason for the particular formulation
2 of PCB that was sold throughout Europe by you when you were O a sales representative?
4 A. Yes. I talked to Mr. Paul Benignus,
5 g_
rr.
g,,
u~s t
6 Q. Did you speak with Mr. Benignus during the
7 time you were a sales rep?
8 A. Yes, I did. 9 Q. Has that in person or viathetelephone or
10 both?
11 A. Both. 12 Q. Hhat did Mr. Benignus tell you was thereason
13 that Monsanto was selling the particular formulations of
14 PCBs in Europe during the time you were a sales representa
15 tive?
16 MR. FEATHERSTOKE: You're now talking about
17 the Py rod or ?
18 MR. BRADLEY: Yes.
19 MR. PE ATEERS TOM Bt Okay. 20 A. Mr. Benignus told me at that point in time 21 that we in Monsanto were making materials that were related 22 to formulations that had been invented by General Electric,
23 and that, as such, the formulations that we were selling, 2 4 if we were to use performance data which had been generated 2 5 in the United States, the formulations had to be aligned
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COMCAKNON a JAEGER
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COMPUTER AIDED TRANSCRIPTION
1 with the formulations that we made tor General Electric in 2 the States* 3 Q. (by Mr. Bradley) Did Mr. Benignus tell you 4 why you would not be selling the specific formulation raade 5 by GE in the States? 6 MR. FEATHERSTORE: You have not established 7 that* I object to the form of the question* 8 Q. (by Mr. Bradley) Go ahead and answer. 9 A* I'd like you to rephrase the question. 10 Q. As I understand it the formulation of Pyroclor 11 that was sold was similar to but not identical to the 12 formulation made by GE in the United States? is that 13 correct? 14 A. Pyranol, as formulated by General Electric,, 15 itself had several formulation forms. They could vary 16 depending on whether fcrlchlorobenzene was used as an 17 additive, whether a tritetra chlorobenzene was used as the 1 8 additive, to the percentage ratio between the chlorinated 19 benzene and the chlorinated biphenyl, and to the concentra 20 tion of the scavenger that I hau talked about, the tetra 21 pnenyl tin. We decided to standardize on one of the formu 22 lations for sale in Europe, which was an exact replication 23 of one of the Pyranol grades sold by General Electric in 24 the United States. 25 Q. Do you recall which of the Pyranol grades sold
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1 in the United States you sold in Europe? 4<r* A. Mor I cion't. But here we* re talking small
3 distinctions between these various grades of product.
4 Q. Was the other formulation that you sold while
5 a sales representative identical to an Inerteen formulation
6 that was manufactured and sold in the United States?
7 A. Yes. The basic difference between the two 8 grades of Pyroclor was in the scavenger that was used. And
9 essentially, the product that we sold in Europe was the 10 same as Inerteen KA, I believe was the designation.
11 Q. Did you receive any training prior to becoming
O
4. iU
a sales representative regarding Pyroclor?
13 A. Once 1 had assumed responsioilIty for sales of
14 p\r roclor, I received training,
15 Q. Where did you receive the training? 16 A. I received some training in Europe and I 17 received some training in the United .States.
18 Q. Was the training just for you, or were you
19 part of a group that was being trained on Pyroclor? 20 A. In terms of sales of dielectric fluids in 21 Europe, at that point in time 1 was the person responsible 22 for selling dielectric fluids in Europe. 23 Q. And I take it, then, the training was directed 24 just towards you when you receiver* training regarding
Lrt Pyroclor?
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1 YOi
2 0, Who gave you
3 A, -- at that time.
4 Q. Ana we!re talking about auring the time that
5 you were a sales representative.
G A. Uh-~huh.
7 Q. In fact, until 1 ask you questions about your
G neat job responsibility, I will assume that all of your
9 answers relate to the work you did as a sales representa
10 tive. Pair enough?
11
1^
i- i-*
Q. All right. vino gave you the training regard
13 ing Pyrocior?
14 A. In Europe I was trained by John Campbell, by
15 Colin Coleman, C-o-l-e-m-a-n, and Richard Baxter.
16 Q. Okay.
17 A. In the United States I received training from
1 B Paul Denignus.
IS Q. What job title did John Campbell have when you
20 received training from him?
21 A. Product supervisor, specialty chemicals.
22 Q. Was John Campbell a medical doctor?
23 A. tto, he wasn't.
2 4 Q, Was he a toxicologist?
25 A. Wo.
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T
JL
Q. Was he an epidemiologist?
2 A. No, he was not.
Q. Was he a businessman?
4 A. Yes, he was. 5 Q. Was hie training in business?
6 A. His training was in science. He adopted a
? business career. 8 Q Do you know whether John Campbell had received
D a doctorate degree when you received training from him? 10 A. John hau received a Doctor of Science degree
il before he trained me,
12 Q. All right. And what job title did Colin
13 Coleman have when you received training from him?
14 A. He was an UTS representative, MTS is a term
13 in Monsanto used to moan Marketing Technical Services. 16 Q. l take it, then, Colin Coleman was not a
17 medical doctor?
16 A. He was not a medical doctor. Be was not a
13 doctor.
20 Q, Nor was ne a toxicologist?
21 A. Ho.
22 q. Nor was he an epidemiologist?
23 A. He was not an epidemiologist.
24 Q. Do youknow whether his educational background
25 was in business?
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1 A. His training was in science. 2 Q. And do you recall what science he received 3 training in? 4 A. Chemistry and physics.
Q. And what job title did Richard Baxter have 6 when you received training from him? 7 A. He v/as manager of research in our laboratory 8 in north Whales, England. 9 Q. Was Richard Baxter a doctor? 10 A. Yes. He was a doctor of science. 11 Q, He was not a medical doctor, then? 12 A. He was not a raeaical doctor, 13 y. Was he a toxicologist. 14 A. Ho, he was not a toxicologist. 15 Q. Was he an epidemiologist? 16 A. Ho. 17 Q. What was his specialty in science? 18 A. Chemistry. 19 Q. Do you know what area of chemistry he 20 specialized in? If there was an area 21 A. Chemical synthesis. 22 Q * What was Paul Benignus*s job title when you 23 received training from him? 24 A. Product manager, dieiectras. r*j -r>J Q. Is Paul Beni gnus a doctor?
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I A. Mo, ho is not. &* 3. Is he a toxicologist? 3 A. Mo, he is not. 4 Q. Is he an epidemiologist? 5 A. No, he is not. 6 Q. Do you know whether his educational background 7 is in business? S A. Yes, it is. 9 q. You indicated that you received training from 10 Mr. Beni gnus in the United States? is that correct? 11 A. 1 want to revisit that question because you 12 asked mo to confine ray comments to the time when I was a 13 sales representative, ana I. don't believe I received 14 training from Paul in the United States while 1 was a sales 15 representative, I certainly met ana was instructed by Paul 16 in Europe curing the time that 1 was a sales represents" 17 t i v o. 1 0 {Thereupon, a short recess was taken.) 19 Q. (by Mr. Bradley) All right. Did you receive 20 any written materials as part of tne training you received 21 from John Campbell, Colin Coleman, Richard Baxter or Paul 22 Benignus regarding Pyroclor? 23 A. I'm sure I did. 2 4 q. Do you recall the nature of the written 23 material that you received from those gentlemen?
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1 A. In the period that I was a sales representa 2 tive I would have received and 1 would have reviewed with 3 them such things as technical literature about the product 4 at that time. I would have received the material related 5 to the maintenance of equipment containing those fluids at 6 that time. I would have received reports about the nature 7 of the marketplace and use of these materials in the 8 European coaiaunity, including Great Britain. That would 9 have included packaging and handling inr'oria&tion surround 10 ing the transportation and storage of these materials. I 11 would have received industrial hygiene information as to 12 now workers in our customers* plants were to use these 13 materials. 14 how, tnat list, I must have you understand at 15 this later stage, is not exhaustive or complete. I 16 probably received information on other subjects, but those 17 specific areas, definitely I would have received and did 18 receive information about. 19 Q. Do you recall the titles of any of the docu 20 ments that you received while a sales rep as part of your 21 training on Pyroclor? 22 h. I would have received the technical literature 23 which I can recall at this date. It was a blue binder of 24 material with a title, "Pyroclor, ** and I would have 25 received copies of a document related to the servicing ana
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1 maintenance of equipment which was called an Askarel 2 Maintenance Guide. Askarel, A-s-Ji-a-r-e~l. **4 Q. What v/as in the blue binder of material 4 entitled "Pyroclor"? 5 A. Information about the areas in which fire6 retardant transformers would be used. It would have 7 contained information about compatible solid elastomeric 8 materials that would be used in the construction of 9 transformers in combination with chlorinated biphenyl 10 liquid dielectrics. 11 Q. What do you mean when you refer to technical 12 literature? 13 A. When I refer to technical literature.. I refer 14 to literature which will define the product in technical 15 terms. It will define the area of application of such 16 chemical products. It will define the relationship between 17 that chemical material and other materials that will be 10 combined with it in chemical application. It will define 19 how the material should be stored and handled. It will 20 include industrial hygiene practice related to the 21 material. It will include disposal methodology for waste 22 materialo. It will include detailed technical specifica 23 tions for the product, and it will probably include, in 24 many cases, relevant codes and industry codes ana standards 25 wnich relate to the material, and it will often contain
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1 chartea Material by the way of charts and graphs which will
o
iLi
relate to the performance properties of the material.
3 In the case of something like Pyroclor, it
4 would include such things as the dielectric strength, tae
5 variation of dielectric strength and temperature, the
6 variation of dielectric strength with the frequency of the
7 power which was being controlled by the transformer.
8 This is an overview of the types of things q that a piece of technical literature related to a chemical
10 insulating fluid would have to portray to the customer, a
11 very wiae range of information involving both the proper
12 ties and tae usage ami handling of that material.
13 Q. Was the technical literature in the blue
14 binder of material entitled "Pyroclor" primarily literature i or* developed in-nouse by Monsanto?
16 A. There certainly was information that was 17 solely generated by Monsanto, but equally, our Pyroclor 18 literature would draw on information that had been
19 generatea by standards and code-setting committees in the
20 United States, and it would give reference and credit to 21 those particular data sources. 22 Q. other than standard and code publications were
23 there any other publications within the binder material
2 4 entitled "Pyroclor* that were not in~house-generated docu
25 ments by Monsanto?
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COMPUTER AIDED TRANSCRIPTION
I MR. PEATHENSTONE % You mean specifically cited 2 in the brochure? Because you have not established that he 3 actually drafted the document. 4 MR. BRADLEY? I assumed that he didn't. He 5 said that he was provided it. 6 MR. FEATHERSTONE; Right. But how would he 7 know what material was looked at to develop this if he 8 aids't uraft it? 9 MR. BRADLEY; I didn't ask him what he -- what 10 material was looked at to draft it. I asked him what was 11 m the blue binder. At least that's what I thought 1 aokeo 12 him. 13 MR. PEATHENSTORE: Okay. Then I make -- 14 Q. (by Hr. Bradley) Okay. Lot me ask the ques 15 tion again. Within the blue binder of material entitle 16 It Pyroclor," was there any other technical literature 17 generated outside Monsanto other than by code-setting 18 groups? 19 A. I think the most direct way I can answer that 20 question is that the Pyroclor literature in Europe was 21 based on the dielectric fluid literature which had been 22 generated by Monsanto in the United States, and that 23 literature had been developed by Monsanto in combination 24 with our customers in the United States. 25 Q. For example, in the blue binder of material
- 27 CONCANMON & JAEGER
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COMPUTER AIDED TRANSCRIPTION
1 entitled "Fyroclor," were there any copies of any studies
done by individuals or groups of people other than Monsanto
3 employees relating to the health and safety of people
4 exposed to PCSs?
5 A. I do n' t recall.
6 Q. Do you recall there being any reference in the
7 blue binder of material entitled "PyroelorH to a 1937
8 round-table discussion that was reported in the Journal of
9 Industrial Hygiene?
10 A. No, I don't.
11 Q, As I understand your testimony, you ceased
12 being the sales representative around 1967?
13 A. It's not clear in lay own raind. At a point in
14 time I was not the sales representative for dielectric
15 fluids. X essentially became the marketing manager for
16 dielectric fluids, replacing John Campbell1s role of the
17 cams period of time. Although I had European-wide
18 responsibility, I was relocating from the United Kingdom to
19 the Brussels headquarters during that period. 20 We moved the European headquarters frora London 21 to Brussels, and essentially I still maintained the same
22 contact and relationship with the European electrical
23 industry, but there had been a subtle shift in my
24 responsibilities from that of purely the sales contact with
o r: tU
the marketplace to rather establishing what our sales and
- 28 -
CONCANNON & JAEGER
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COMPUTER AIDED TRANSCRIPTION
1 uerr oraance strategy tor that particular product lino was 2 in Europe, 3 Q. And when you became marketing manager; did the 4 blue binder of material entitle "Pyroelor" still exist? 5 A, Yes, it did. 6 0. Did you use -- Let me rephrase the question, 7 During the time that you were marketing manager did you 8 maintain the blue binder of material entitle wPy roelor'1? 3 A. We maintained technical literature relative to 1 0 the use and handling of Pyroelor. Whether it remained blue 11 daring that whole period, I really don't remember, 12 MR. BRADLEYt Could you read back that answer, 13 pi ease ? 14 (Thereupon, the reporter read back the answer.) 15 Q. (by Mr. Bradley) Did you have files of 16 literature on PCBs during the time that you were sales 17 representative, other than materials contained in the blue 1 8 binder entitled "Pyroelor"? IS A. Would you repeat that question, please? 20 Q. Did you have materials on PCBs during the 21 period of time you were sales representative, other than 22 the material that was in the blue binder entitled 23 "Pyroelor"? 2 4 A. We would have had equivalent literature which 25 related to the use of the Aroclor family of products in
- 29 CONCANNON & JAEGER
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COMPUTER AIDED TRANSCRIPTION
1 capacitors* We would have in certain situations made use > of American literature. 3 Q. Okay. 4 A. And our market technical service group would 5 prepare specific project reports on issues which were 6 raised by specific customers relative to their individual 7 use of our materials. 8 Q. And this was all material that you would have 9 maintained but would not have been within the blue binder 10 of material entitled "Pyroclor"? 11 A. This is true. 12 Q. And where was thisliterature or --Excuse me. 13 Where was this material kept? 14 A. Copies of this literature would be kept in our 13 -- certainly it was maintained in our Brussels office. But X t in our regional sales offices, people would have access to 17 sets of that data to send to both current and prospective 18 customer s. 19 mi. PSATHERSTOHE: We* re now switching between 20 the time period that you were sales rep and the time period 21 you were marketing manager, because you just now made 22 reference to the Brussels office. 23 A. Uh-huh. I thought we had already made that 24 b ridge, any way. 2 5 q. (by Mr. Bradley) All right. So that I under
- 30 CONCAWNON h JAEGER
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COMPUTER AIDED TRANSCRIPTION
1 stand your answer, the period of time that you had the 2 literature outside of the blue binder of material entitled 3 tt?yroclor" was during the time you were marketing manager? 4 A. We had literature about our products throughTM 5 out the period when I was sales representative and when I 6 wa3 marketing manager. 1 Q. And the separate set of documents that were in 8 existence while you were sales rep were maintained where? y A. At that particular time when I was a sales xG rep, our European headquarter office was in London, and the 11 main literature center was at that time in London. When v/e12 mcved the European headquarters from London to Brussels, 13 then our central literature source would be maintained in 14 Brussels, not in London. But all sales offices would have 15 access and would have a more limited storage of technical 16 literature for product which they were selling in that 1? particular region, and if their particular region contained 18 customers of dielectric fluias, that regional office would 19 have copies of the dielectric literature. 20 Q. Okay. Whileyou were sales representative, 21 did Monsanto have a medical department in its European 22 operations? 23 A. Yes, we did. 2 4 Q, And where was it located? 25 A. In London.
- 31 CONCANNON & JAEGER
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COMPUTER AIDED TRANSCRIPTION
1 Q. while you were saxes representative, who was 2 the head of the medical department in London tor Monsanto? -* A. We had a medical department which had a number 4 of functions. One was that purely of having a medical 5 office in a headquarters* building to look after strictly 6 personnel medical affairs. We equally had associated with 7 that department an individual who was responsible for 8 product issues of a medical nature, but that latter func 9 tion operated as an extension of the headquarters product 10 safety groups in the United States. 11 Q. During the time you were sales representative, 12 who was the person within Monsanto's medical department in 13 London responsible for product issues of a modi cal nature? 14 A. Doug Hardy, H-a-r-d-y. 15 Q. At the time you were sales representative, do 16 you know whether the Monsanto headquarters product safety 17 group in the United States was run by a medical doctor? 18 HR. FEATHERSTONE: Sorry. Hay I hear the 19 question again, please? 20 (Thereupon, the reporter read back the question.) 21 A. No, I don't. 22 Q. (by Mr, Bradley) While sales representative, 23 do you know whether the Monsanto headquarters product 24 safety group in the United States was run by a toxicolo 2 5 gist?
- 32 CONCANNON & JAEGER
~ ~ WATER- PC EhS D0000056472
COMPUTER AIDED TRANSCRIPTION
1 A. No, I don`t. 2 Q. Do you know whether the person in charge or 3 the headquarters product safety group in the 0.S., while 4 you were sales rep, was an epidemiologist? 5 A. No, I don't. 6 Q. Do you know whether, while you were sales rep, 7 the person in charge of the Monsanto headquarters product 8 safety group in the United States had any training whatso 3 ever in the medical and toxicological aspects of 10 polychlorinated bipheny1s? 11 A. No, I don't. 12 Q. While you were sales representative, did you 13 ever hear the term "business group" in relation to the 14 manufacture and sale of polychlorinated biphenyls? 13 A. Can you repeat that question? 1C MR. BRADLEY: Would you read it? 17 (Thereupon, the reporter read back the question.) 18 A. Yes. 19 Q. (by Mr. Bradley) Was the product safety group 20 at Monsanto"s headquarters in the United States part of the 21 business group working with Monsanto products containing 22 PCB s? 23 A. Mo. 2 4 Q. While you were sales rep, what persons by 25 title or name were part of the business group working with
- 33 COMCAMMOM & JAEGER
COMPUTER AIDED THAI! SCR I FI ION
1 Monsanto products that contained PCBs? 2 A. Whilst I was a sales representative with 3 Monsanto in Europe, ny contact in the United States in the 4 business group was Paul Benignus. 5 Q* Did Hr. Benignus indicate to you who else, if 6 anyone, was part of the business group relating to Monsanto 7 products containing PCBs? 8 A. To the extent that Paul Beni gnus himself re 9 ported to supervisory management within a broader business 10 division than dielectric chlorinated biphenyls, there were 11 people senior to Mr. Beni gnus who had management responsi 12 bility for a range of products, including the chlorinated 13 biphenyl dielectros. 14 Specifically, since you asked me to be 15 specific, we would be visited occasionally in Europe by Hr. 16 George Buchanan, who was responsible for the specialty 17 products area, or he may at that time have been called the 18 function fluid business within the organic division, and 19 within whose group Hr. Benignus worked. 20 Q, Did Hr. Beni gnus indicate to you that his 21 supervisor was part of the business group for Monsanto 22 products that contained PCBs? 23 A. Yes. 24 Q. Did Hr. Benignus indicate to you anyone else 25 who was part of the business group for Monsanto products
- 34 CONCANNQN & JAEGER
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COMPUTER AIDED TRANSCRIPTION
1 containing PCBs? 2 A. In the United States? 3 Q. Yes* 4 A. Dr. Ralph Munch, H-u~n~c-h, was responsible 5 for the technology, the applicational technology of the- PCS 6 fluids at that point in time, 7 Q. And Mr. Benignus indicated to you that Dr, 8 Munch was part of the business group for Monsanto products 9 that contained PCBs? 10 A Yes. 11 Q* ifno else, if anyone, did Mr. -- 12 MR. FEATHERSTONE: Are you talking about 13 ciiel ectr ies, David? 14 MR. BRADLEY: Isn talking about dielectrics. 13 MR. FEATHERSTONE s He* s talking asoout products 10 containing PCBs. So, Mr* Bradley, are you talking about 17 dielectrics, or are you broadening this? 10 Q. (by Kr. Bradley) So that I understand your IS answer, your answer is related to dielectric products 20 manufactured by Monsanto that contained PCBs? is that 21 correct? 22 A. As was related to dielectric fluids. 23 Q. All right. Did Mr. Benignus indicate to you 2 4 who else was a part of the business group working within 25 Monsanto for dielectric products containing PCBs?
- 35 COMCAMROM & JAEGER
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COMPUTER AIDED TRAH3CRIPTIGN
X A. At the time that I was a sales representative 2 the only two people I had contact with and that l wae aware 3 o as being members of the dielectrics business group for 4 fluids including chlorinated biphenyls were Paul Benignus 5 himself and Dr. Munch. 6 Q. Was there the business group -- Bet me 7 rephrase it. Vlas there a European business group for 8 dielectric products manufactured by Monsanto that contained 9 PCBs? 1C A. It was not referred to as a dielectric busi 11 ness group. I mean, the business in Europe was managed by 12 -- At the time that I was sales representative, essential 13 ly, dielectric fluids in Europe in a commercial management 14 sense were managed by John Campbell. I was the salesman, 15 and Colin Coleman was the technical service representative. 16 Q. When you have -- Do you consider poiycnlori17 nated terphenyls to he part of the group of polychlorinated 1 8 biphenyls? 19 A. I'd ask you to repeat that question, please. 20 Q. Do you consider polychlorinated terphenyls to 21 be part of the group known as polychlorinated biphenyls? 22 A. No. 23 Q. Did Monsanto manufacture products sold 24 throughout Europe while you were sales representative that 25 contained polychlorinated terphenyls?
-- 36 CONCAWMOM & JAEGER
WATER PCB-SD0000056476
COMPUTER AIDED TRANSCRIPTION
1 A. Monsanto manufactured a number of poly chlori 2 nated terphenyls, but they were part of the polychlorinated 3 polyphenol family, There is no way that you can -- A 4 polychlorinated biphenyl by definition cannot be a 5 polychlorinated terphenyl, and vice versa. 6 Q. And you indicated that they' re all part of the 7 polychlorinated polybiphenyl family? 8 A. Mo. No. 9 Q. That'b why I asked. 10 A. I said that, if you begin to link benzene 11 rings together, at one point or juncture, one is a phenyl 12 group, two is a biphenyl group, three is a terphenyl group, 13 four is a quatraphenyl group. So, something which contains 14 three rings can never be a biphenyl. Something that con 15 tains two rings cannot be a terphenyl. That terminology 16 discretely defines the difference between the number of 17 rings you nave in the particular molecule. Tou can combine 18 and cover the whole group by a descriptor which is not 19 widely used which is a polyphenol. 20 Q. At the tirae that you were a sales rep, did the 21 Monsanto corporate headquarters in the United States have a 22 medical department? 23 A. I'm sorry? 24 Q. At the time that you were a sales representa 2 5 tive, did the Monsanto corporate headquarters in the United
- 37 COM CANNON & JAEGER
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COMPUTER AIDED TRANSCRIPTION
X States have a medical department? 2 A. I don't know. 3 Q. Does Monsanto still have a corporate head 4 quarters in Brussels? 5 A. Monsanto has its European headquarters of its 6 agricultural company and its chemical group in Brussels. 7 Q. Do you know whether the European headquarters 8 for Monsanto in Brussels still maintains files of material 9 it had on PCBs? 10 A. I do not know whether the company consolidated 11 records about PCBs in Europe within Europe or whether we 12 combined those records in our consolidated PCB records in 13 St. Louis. 14 Q, And if they ware consolidated within Europe, 15 they would be at the headquarters in Brussels? 16 A. I don't know. 17 Q. Did you receive any additional training in IS Pyroclor when you became marketing manager for dielectric 19 1 ui ds? 20 A. The time that they changed ray responsibili 21 ties from sales representative to that of marketing mana 22 ger, I* m not conscious that I received any specific addi 23 tional training. 24 The reason for my appointment to the marketing 23 management role was essentially because of the experience
- 38 CONCANNOM JAEGER
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COMPUTER AIDED TRANSCRIPTION
1 that I had gained in being the sales representative for 2 those materials. And so, if education includes that period 3 of osmosis of learning on the job, yes, I received more 4 training. 5 Q, Do you recall whether you received any addi 6 tional written material specifically directed towards 7 Py rod or when you became marketing manager for dielectric 8 fluids? 9 A. As we developed and updated technical litera 10 ture, 1 would receive new materials and new additional 11 material to include in further additions of our technical 12 literature, 13 A piece of technical literature is not static. 14 As your knowledge evolves, so does -- you update your 1 K technical literature. 16 Q. Would the technical literature that was 17 evolving include instruction manuals for customers purchas 18 ing Monsanto products containing PCBs? 19 A. Yes, it would. 20 Q. Did the EuropeanMonsanto instruction manuals 21 differ from instruction manuals distributed by Monsanto to 22 its customers within the United States? 23 MR. FEATHERSTONE} Object to the form of the 2 4 question. It*s vague and indefinite. 2 $ A. I`11 answer it.
- 39 COMCANMOM & JAEGER
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COMPUTER AIDED TRANSCRIPTIOH
i Our American literature was in the American 2 form of the English language. Our European literal was in 3 several languages, including British English. 4 Q. (by Mr. Bradley) Would the European instruc 5 tion manual simply take the English versions developed by 6 Monsanto's corporate headquarters in the United States and 7 translate them into various languages? 8 MR. FEATHERSTONES Object to the form of the 3 question. Also vague, 10 A, Would you care to rephrase the question? 11 Q. (by Mr. Bradley) Yeah. When -- Do you know 12 whether the instruction manuals that were sent to customers 13 of Monsanto's European operations received instruction 14 booklets that were identical to the instruction booklets 15 distributed to Monsanto's customers in the United States, 16 with the exception that they were simply written in another 17 language ? 18 A. By extension of the definition of "other 19 language," you need to appreciate that technology is itself 20 a language. So that, to the extent that some of our 21 European customers were advanced enough to use a different 22 system of measurement, the metric system, there was not 23 just translation, of language to language. Charts, graphs, 2 4 tables would neoa to be changed frora the duodecimal system 25 operated in the United States to the more broadly used
- 40 CON CAN 13 OH & JAEGER
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COMPOSER AIDED TRANSCRIPTION
1 metric systems. roir In terms of standardlyation, where material 3 standards in Europe differed from the hSTll standards 4 exercised in the United States, then the relevant national 5 standards, such as BXK in Germany or the British Standards 6 Institute in Britain, would need to be checked, and we 7 would need to cnange the material content so that it 8 related to that particular national emphasis. Even then, S Monsanto was strategicing globally and acting locally. 10 Q. so as I understand it, the differences were in 11 --- involved conversion of the measuring system in the 12 United States to the metric system. That was one change in 13 the instruction booklet? is that correct? 14 A. Yes. 15 Q. And another change came about if there were 16 different code-setting standards in different nations? 17 A. This is true. 18 Q. Were there any otherchanges? 19 A. Probably, yes. 20 Q. And what were they? 21 A. X don't recall minute by minute everything 22 that happened twenty years ago. I* m sorry. 23 Q, Of course I don't expect you to recall every 24 thing in detail, but I'm interested in what you do recall. 25 Who would know -- Let me rephrase it. Who, if
- 41 COMCAMNON & JAEGER
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COMPUTER AIDED TRANSCRIPTION
1 anyone, was in charge within Monsanto* a European operation *? for development of the instructions manuals that 3 accompanied Monsanto products containing PCBs that were 4 cold throughout Europe? 5 A. At that stage the procedure, as I -- Now, are 6 we talking about -- am I a sales representative or am I a 7 marketing manager? 8 Q. Sales rep, 9 A. Okay. When I am sales rep, then John 10 Campbell, as the marketing manager, would be responsible 11 for clearing any new literature before it was public and 12 issued to our cus!tomer base. He would make sure that our 13 technology as represented by Richard Baxter and Colin 14 Coleman had signed off, that they agreed that the technical 15 information contained therein was accurate and was 16 expressed correctly in units. There would be a sign off by 17 Doug Hardy in terms of saying that he agreed that the 18 representation for material handling Instructions were IS essentially suitable for under standing in Europe. 20 Q. And whan you became marketing manager, did you 21 have the role that previously Mr. Campbell had? 22 A. Dr. Campbell. 23 Q. Dr. Campbell. 24 A. Yes, I did. 25 q. And when you undertook that responsibility as
- 42 CONCANNON & JAEGER
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1 marketing raanagsr, did you review any medical or toxico 2 logical information relating to PCBs? 3 A. Purely for clarification are we going to be 4 jumping back and forth at this point between my marketing 5 management role or my sales representative role, or -- In 6 terms of my trying to openly answer your questions, it 7 really would be helpful if I know what period I'm answering B from, because my role changed, as I said, and I need to 9 know what role I'm in if I'm going to be responsive to your 10 questions. 11 Q, I apologise if ray question wasn't clear, I 12 thought my question started by when you were marketing 13 manager, but if it didn't, that's what I intended. 14 So, while you were marketing manager, did you X 5 * review any material relating to the medical or 16 toxicological issues involving PCBs prior to your work with 17 updating instruction manuals? 18 A, I was not qualified to comment on the handling 19 and industrial hygiene materials. Personally, it was my 20 responsibilifcy to make sure that literature that we were 21 going to be sending to the marketplace had received review 22 in Europe from Doug Hardy as to his under standing that this 23 was an appropriate representation of the safety of that 2 4 product and the handling of that material. And if he 2 5 required to ask questions of his contacts in the United
- 43 CONCAMSON & JAEGER
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COMPUTER AIDED TRANSCRIPTION
1 States, then he would so do. 2 Q. Do you know whether Doug Hardy was relying on 3 information forgiven to him by Monsanto employees in the 4 United States when he reviewed the proposed changes, if 5 there were any, to instruction manuals? 6 A. Okay. Now, am I marketing manager? 7 Q. Yes. 8 A. Marketing manager. Okay. At that time I know 9 that Doug Hardy would make his judgments about material in 10 Europe based on his view of what he was receiving from his 11 peers in the United states, and individual contacts that he 12 would make within the Monsanto technical community as 13 opposed to the commercial community, and outside of the 14 Monsanto technical community in the European technical 15 comrauni ty. 16 Q When you refer to "his peers," do you mean his 17 peers within the Monsanto corporate headquarters in the 18 United States? 19 A. Yes. Doug Hardy was seeking to find out how 20 to -- what was the United States view of handling materials 21 made by Monsanto. Protocol suggested he should elicit such 22 information from his peers within Monsanto. 23 Q* Was Doug Hardy's role different at all during 24 the period of time when you were sales rep versus when you 25 were marketing manager regarding that one issue we've just
-44CONCANNON & JAEGER
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COMPUTER AIDED TRANSCRIPTION
1 discussed? 2 A. 13ot considerably different. 3 MR. BRADLEY: If it's acceptable, this would 4 be a good time for me to be taking a break. Ten minutes. 5 (Thereupon, a short recess was taken, after which 6 the reporter read back the last question.) 7 A, Not considerably different. UCS Q. (by Hr. Bradley) I take it, during the time 3 you were marketing manager, that you submitted changes in 10 instruction manuals to Doug Hardy for his review for 11 products containing PCBs? 12 A. Yes, 13 Q. Did you send a letter to Mr. Hardy requesting 14 that he review those changes in the instruction manuals? 15 A. It. would have been normal practice that, if a 16 draft change of any sort had been suggested, proposed, that 17 I would send a copy to Hardy's office and say, "Heed your 18 commentary on this suggested change." 19 Q Okay. And would Doug Hardy then provide you 20 with written comments regarding any suggested changes? 21 A. It would have been the appropriate action for 22 him to take, yea. 23 Q. Do you recall whether he, whether Doug Hardy 2 4 ever provided my written material to you regarding any of 25 the proposed changes in instruction manuals for products
- 45 COHCANNOH a JAEGER
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COMPUTER AIDED T RAD SCRIPTION
1 containing PCBs?
2 A. Specifically, no.
3 Q. What was your job title following your being
4 marketing manager?
5 A. I became marketing manager, food and fine
6 chemicals.
7 Q, When did you become marketing manager for food
8 anu 1 ne ch em i cal s ? 9 A. 1970 slash *71.
10 Q. When you became marketing manager for food and
11 fine chemicals, did you have any responsibility for
12 dielectric fluids containing PCBs?
13 A. I did not,
14 Q, What fine chemicals were you responsible for
15 when you became marketing manager for food and fine
16 chemical a? 17 A. The major product area for which I had
18 responsibility was for the marketing of aspirin.
19
Q. What was
your next job title?
20 A. Afterthe food-and-fine job?
21 Q. Yes.
22 A. Hy next job title was international sales
23 mansger, fluids. 24 Q, When did you become international sales
2 5 manager, fluids?
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COMPUTER AIDED TRANSCRIPTION
1 A 1 97 4 + Q. As internationalsales manager for fluids, did 3 you have any responsibility for dielectric fluids contain 4 ing BCB s ? 5 A, Yesf I did. 6 0. What responsibilities didyou have? 7 A, I had the responsibility to manage the sale of 8 dielectric fluids containing PCBs in marketplaces outside 9 of the United States, around the rest of the world, as part 10 of a product range of functional fluids, which included 11 aviation fluids, industrial heating fluids. So it was one 12 product line component of a product line tor which I had a 13 responsibility for sales outside of Worth America. 14 Q. Okay. 15 A. And that job was based inAmerica. 16 Q. As international sales manager for fluids, did 17 you have any responsibility for selling transformers or 18 capacitors containing PCBs? I mean -- Strike the question. 19 As International sales manager for fluids, did 20 you have responsibility for selling any Monsanto products 21 that were intended for use in electrical transformers or 22 capacitors to be used by the electrical industry? 23 A. Yes, I did. 2 4 q. What were you selling in that regard? 25 A. I was selling Pyroclor, I was selling
- 47 CONCANNON & JAEGER
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COMPUTER AIDED TRANSCRIPTION
1 Inerteen, and I was selling Pyranol. 2 Q. Was the Inerteen that you were selling manu 3 factured by Monsanto? 4 A. Yea, it was. 5 Q, Was it manufactured on -- in plants owned ana 6 operated by Monsanto? 7 A. Yes, it was. 8 Q. Was the Pyranol you were selling manufactured 9 by Monsanto? 10 A. Yes, it was. 11 Q. And was it manufactured in plants owned and 12 operated by Monsanto?
.}
13 A. Yes, it was. 14 Q, And wore those plants that manufactured 15 Pyranol within the United States? 16 A. The plants that manufactured the Inerteon and 17 Pyranol that I sold were in the United States. If I were 18 selling Pyroclor, then it would have been manufactured in 19 our British plant. 20 Q. As international sales manager for fluids, did 21 you have any responsibilities regarding instruction manuals 22 that accompanied products manufactured by Monsanto that 23 contained PCBs and were dielectric fluids? 2 4 A. My responsibility as sales manager of fluids 25 would be to insure that any customer or perspective
- 48 CONCANNON & JAEGER
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COMPUTER AIDED TRANSCRIPTION
1 customer in ray geographical area of responsibility had 2 received a copy of our instruction manuals. It would not 3 have had -- My job at that stage did not contain a 4 responsibility for actually producing the instruction 5 manuals. 6 Q. While you were international sales manager for 7 fluids, who within Monsanto was responsibility for produc 8 ing the instruction manuals for Monsanto dielectric fluids 9 containing PCBs? 10 A. Paul Benignus. 11 Q, Do you know how long Mr. Benignus had that 12 respond bii ity ? 13 A. At the time that I was in the international 14 salesraan management job in 1974, Mr. Beni gnus had certainly 15 been responsible for the dielectric fluid line for 16 materials containing chlorinated biphenyls for at least ten 17 years, 18 Q. And did those responsibilities that Mr. 19 Beni gnus had include determining what would be contained 20 within the instruction manuals accompanying Monsanto 21 dielectric -- Monsanto products containing dielectric 22 fluids with PCBs? 23 MR. FEATHERSTONES Well, I think you had it 24 right the first time, which was Monsanto dielectric fluids. 2 3 You said Monsanto products containing dielectric fluids.
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COMPUTER AIDED TRANSCRIPTION
1 Q. (by Mr. Bradley) Let me re--ask the question. 2 Did Mr. Benignus have responsibility during that ten-year 3 period for determining what would he included in the 4 instruction manuals for Monsanto dielectric fluids 5 containing PCBs? 6 A. As product manager, he would have respondTM 7 biiity for issuing instruction manuals. He would be guided 8 as to content of certain chapters of the instruction book 9 by inputs from other disciplines within Monsanto. 10 Q. And after he received that guidance, the final li decision, though, was his? 12 A. Ho. He could not -- If for example, our 13 technology department insisted that certain dielectric 14 performance data were included, he could not preclude them 15 and say, "Mo, we1 re not going to include that." So he had 16 responsibility for making sure that Monsanto had in its 17 marketplaces technical support literature relative to our 13 products. He would have to obtain clearance that such 19 literature followed corporate guidelines beyond just his 20 product authority relative to certain areas of contact. 21 Q. I want to take you back in time to 197 0. 22 Whatever your job title was doesn't matter to me, 23 A. Okay. 24 Q. In 1970 were there any European nations that 2 5 had proposed elimination of PCBs?
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COMPUTER AIDED TRAMSCRIPTION
1 MR. FEATHERSTOME: Object to the form of the 2 question. 3 A. Could you ask the question -- 4 Q. (by Mr. Bradley) I will re-ask it. In 1970 5 had any European nations outlawed the use of PCBs? 6 A. Mot to my knowledge. 7 Q. In 1970 had any European nation proposed -- 8 Let me rephrase it. In 1970 had there been proposed 9 legislation in any European nation that would restrict or 10 eliminate the use of PCBs? 11 A. Mo. 12 Q. In 1971 was there any European nation that had 13 legislation restricting or eliminating the use of PCBs? 14 A. Hot to my knowledge. 15 Q. Was there ever a time when any European nation 16 enacted legislation restricting or eliminating the use of 17 PCD S ? 18 A. I ara not aware of any point when my job within 19 Monsanto contained responsibility for fluids associated 20 with PCBs or through my general knowledge of anything that 21 be happening whilst my job was not related to PCBs, of any 22 European country that went as far as early, in terms of 23 regulating PCBs, as the United States of America. 2 4 Q. Didn't Sweden take any regulatory action 25 r el citing to PCBs during the 197 0s?
- 51 COMCANNOK & JAEGER
" "WATER PCFSDb000056491
COMPUTER AIDED TSAllBCR1PT1011
1 A. I can't talk for the whole of the 1270s, 2 Decause 1 was not involved with PCBs during the totality of 3 the 1970s. 4 Q. When did you cease your involvement with PCBs 5 during the period of the 1970s? 6 A. In 1977 . 7 Q, By 1977 had Sweden taken any action to 8 restrict or eliminate the use of PCBs? 9 A. Sweden may -- I do not specifically know. If 10 there were anything going on in Sweden at that point in 11 time, it was probably going to be regulating the use or 12 restricting the use, but I am not specifically aware of 13 Swedish regulations concerning the use of PCBs. 14 Q. So that I understand your answer -- I'm not so IS much interested in what your specific knowledge is of 16 specific regulations in Sweden regarding the use of PCBs, 17 but I am interested in knowing if you know when Sweden 1 8 first enacted regulations, if it ever did, restricting or 19 eliminating the use of PCBs. 20 A. I am not aware of any regulations issued by 21 Swedish authorities reference the use of PCBs. 22 Q. And when I say "regulations," I include laws 23 in that. Is that your understanding? 24 A. Yes. 25 Q. Okay. Prior to 1977 did Japan enact any laws
- 52 CGHCAUHON & JAEGER
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COMPUTER AIDED TRANSCRIPTION
1 or regulations restricting or eliminating the use of PCBs? 2 A. For clarification may I ask whether we're 3 talking about dielectric situations or generic uses of
4 PCBs? 5 Q.
Generic uses of PCBs.
6 A. I believe that Japan did issue regulations 7 concerning the use of PCBs, excluding them from certain
8 appiications. 9 Q. And when do you believe that Japan took that
10 action? 11 A. 12 Q,
In the seventies. In the early, mid, or late seventies? If you
13 know.
14 A. Early to mid. 15 Q. Do you know whether the restrictions imposed IS oy Japan on PCBs included restrictions on PCBs in 17 dielectric fluids? 18 A. 1 believe it did not. 19 Q. Did Great Britain prior to 1977 enact any laws 20 or regulations restricting or eliminating the use of PCBs? 21 A. I am not aware of regulations in Great Britain 22 restricting the use of PCBs generically or limiting the use 23 of PCBs generically. At that point in time Monsanto was 24 only involved in dielectric uses of PCBs. 2 5 There were regulations passed in a number of
- 53 -
C0NCA1-JN01J & JAEGER
WATER PCB-SD0000056493
COMPUTER AIDED TRANSCRIPTIOK
i countries alter the fact of Monsanto's withdrawal from 2 certain nonelectrical applications, Again, I'm not sure of 3 details because they were irrelevant to us, because, in the 4 1970b, essentially, Monsanto at a point in time was only 5 involved with dielectric uses of PCBs. 6 Q. When did you cease being international sales 7 manager for fluids? 6 A. Late 1974, early 1975. 9 Q. So you had that job for about a year? 10 A. About a year. 11 Q. What was your nextjob title? 12 A. I was manager of dielectric fluids. 13 Q. Did that job begin in 1975? 14 A. It was either November or December of 1974, or 15 January of 1975; it was about the turn of the year, 16 Q. Did you receive any additional training re 17 garding PCBs when you became manager ofdielectricfluids? 18 A. Yes, X did. 19 Q. What trainingdid you receive? 20 A. Informal training. 21 Q. Prom whom? 22 A. From Paul Beni gnus; frora my immediate super 23 visor, Dr. Paton, P~a-t-o-n; from the research departments 24 within Monsanto; and from people who were involved with 25 Monsanto's positions relative to the use and application of
- 54 CONCAMMOM & JAEGER
WATER PCB-SD0000056494
COMPUTER AIDED TRANSCRIPTION
1 PCSs, such as Mr. Papageorge, p-a-p-a-g-e-o-r-g-e. 2 Q. Okay. 3 A. And again, that list Is a list of significant 4 people who talked to me at the time that I changed -- I 5 made that transition. It is not exhaustive. 6 Q. What -- I want you to tell roe as much as you 7 can remember about the content of your discussions with Mr. 8 Papayeorge as part of your informal training when you S became manager of dielectric fluids, 10 MR, FEATHERSTONE: That's the question? 11 HR. BRADLEY: Yes. 12 THE WITNESS: Can I talk to Chris a moment? 13 HR. BRADLEY s Ye S. 14 (Thereupon, a short colloquy was had, after which 15 the reporter propounded the previous question.) 16 A. The informal training essentially was a day17 to-day process; there would be very few days that I would 18 not be talking with Bill Papageorge. 19 The nature of the dielectrics business in the 20 United States and beyond the United States was such at that 21 point in time that we were routinely communicating with our 22 customers, with the users of electric equipment, with 23 regulators, with universities, and as such, very few days 24 would go by that I would not have occasion to discuss 25 emerging situations with Hr. Papageorge, and to the extent
CONCANNON & JAEGER WATER PCB-SD0000056495
COMPUTER AIDED TRANSCRIPTION
1 that, in the coarse or those discussions I would learn 2 tilings that I had not been knowledgeable or previously, it 3 was part of rny education. 4 Q. (by Mr. Bradley) So your informal training 5 with Mr. Papageorge is what you learned primarily from your 6 day-to-day contacts with him? 7 A, Yes, it was. 8 Q. You indicated that, because of the nature of 9 the dielectric fluids during the period of time you were 10 manager of dielectric fluids, that you would -- Excuse me 11 -- that Monsanto would routinely have communications with 12 customers! is that correct? Is that what you said? 13 MR. FEATHERSTONE* He said "Mature of the 14 dielectrics business." 15 MR. B RADLEY: Wha t ev er. 16 Is it true that, because of the nature of the 17 dielectric business when you were manager of dielectric 1G fluids, that Monsanto would be routinely communicating with 19 customer a? 20 A. We were routinely communicating with customers 21 throughout the period that I was manager of dielectrics. 22 Q. (by Mr. Bradley) Did those customers include 23 General Electric? 24 A. Yes. 25 Q. Did they include Westinghoust?
- 56 CORCANNON & JAEGER
WATER PCB-SD0000056496
COMPUTER AIDED TRANSCRIPTXQH
1 A. Yes. 2 Q. You also indicated that, because of the nature 3 of the dielectric business while you were manager of the 4 dielectric fluids, that Monsanto would have conuaunications 5 with users of dielectric equipment; is that correct? 6 A. Monsanto had communications with users of 7 dielectric equipment. By virtue of our membership with 8 certain industrial panels, and at the request of our direct 3 customers, frora time to time we would have communication 10 sessions with their customers. And through processers and 11 repairers of electrical equipment, we would have contact 12 v/ith our customers* customers. Through participation in 13 EPA panels, we would have contact with our customers* 14 customers. 15 There were many ways during the period that I 16 was manager of dielectrics that Monsanto, myself, and more 17 broadly, other people within Monsanto, were in contact ana 18 communicating with not only our direct customers, but their 19 customers, and other people involved in PCB considerations. 20 Q. what industrial panels was Monsanto a member 21 of that resulted in Monsanto communicating with users of 22 ciielectrical equipment? 23 A. There were groups such as the ANSI C107 2 4 committee, the EPRI, Electrical Power Research Institute, 25 national Electrical Manufacturers Association, Edison
- 57 concalinon & jaeger
WATER PCB-SD0000056497
COMPUTER AIDED TRANSCRIPTION
1 Institute. 2 Q. Is that Edison Electrical Institute, EEI? 3 A. Yes. 4 There were various conferences which were 5 specifically summoned to relate to PCBs. There was an SPA6 sponsored convention that related to these PCBs. 7 Q. Was that in Chicago in 1975? 8 A. Yes, it was. Widely attended by a broad 9 representation of the electrical industry. 10 Q. What leads you to that conclusion, that it was 11 broadly represented by the members of the electrical 12 industry ? 13 A. I was a speaker at the conference ? I know what 14 the attendance at the conference was. 15 Q. How do you know what the attendance was? By 16 speaking with people who were also in attendance? 17 A. Yes. 18 Q. And how else do you know whether there were 19 members of the electrical utility industry at the 1975 20 coni' erence? 21 A. Because that convention was convened by the 22 EPA to keep people aware of how the convention was being 23 publicised and how it was being positioned, and I know that 2 4 the EP?* sought a strong attendance from the- utility 2 5 industry.
- 58 CONCANNON & JAEGER
WATER PCB-SD0000056498
COMPUTER AIDED TRAMSCRIPTION
1 Q. Any other way that you know that members or 9 the electrical utility industry were present at that 1975 3 conference? 4 A. I guess at the time of the convention and 5 shortly thereafter we had some discussions regarding who 6 had been there, and short of reviewing any sign-up list for 7 the convention, I mean, I was aware that there had been a 8 fairly broad representation of the utility industry. 9 Q. Did you personally review the sign-up list? 10 A. No, 1 did not. 11 Q. Who did you speak with at the conference who 12 indicated to you they were a member of the electrical 13 utility industry? if you recall. 14 A. I don't -- I talked to an enormous number of 13 people at that convention. 1C Q. Well, do you recall whether any of them *X -/7 informed you that they were a customer of General Electric? 10 A. Nobody advised me specifically that they were 19 a customer of General Electric. Many of them told me that 20 they were .members of various United States utility corpora 21 tions and they bought electrical equipment containing PCSs, 22 which was the subject of the conference. 23 Q. Were there written proceedings of the 2 4 conference following its eorapletion?
A, Yes, there were. - 59 -
_____________
WATER PCB-SD0000056499
COMPUTER AIDED TRANSCRIPTION
1 Q. Do you know whether those were mailed to ou electrical utility industries that purchased dielectric 3 fluids containing PCBs that were nanufacfcured by Monsanto? 4 A, I know that we mailed copies of my papers -- 5 ray paper at that conference to a number of utility people 6 who said that either they had been and had not managed to 7 get a copy at the conference or had heard of the conference 8 and requested a copy of the paper. In terras of saying, 9 "Was there a Monsanto mailing of the proceedings of that 10 conference to our customers* customers," no, there was not, 11 Xt was not our conference? it was an SPA conference, 12 Q. Do you know whether -- Let me ask it this way:
\ 13 Wo know Monsanto didn't do the mass mailing. Do you know 14 whether HPA did a raailing of the proceedings of that 15 conference to your customers' customers? 16 A. I know that they had the proceedings available 17 to those who requested it. 18 Q, You also indicated that you received Informal 19 training when you became manager of dielectric fluids from 20 different research departments within Monsanto. Which 21 research departments did you receive informal training from 22 when you became manager of dielectric fluids? 23 A. I received -- Again, I routinely communicated 24 with our dielectric technology group, headed by Ralph 2 5 Munch. I communicated with our analytical services depart
- 60 CON CANNON ft JAEGER
WATER PCB-SD0000056500
COMPUTER AIDED T R Mi SCRIPT! 013
1 went, specifically with Jim Muir at that time, and, as 1
r\ nave said previously, 1 communicated routinely with Bill
3 Papageorge, representing the outreach from ray particular
4 role into the toxicology and medical group of Monsanto.
5 Q. So Bill Papageorge, as I understand your last
6 answer, was your connection to Monsanto's medical and
7 toxicology departments while you were manager of dielectric
8 f1uius?
9 A. He was my major contact with those depart-
10 ments
11 Q* Who was director of Monsanto's medical depart
12 ment when you were manager of dielectric fluids?
13 A. George Roush.
14 Q, Did you discuss anything with George Roush
15 while you were manager or dielectric fluids regarding the
16 medical or toxicological aspects of PCBs?
17 A. Prom time to time, yes.
18 Q. Tell rae what you remember aboutthose conver
IS sations.
20 ME. FEATHERSTONE: With Dr. Roush?
21 MR. BRADLETs Yes.
22
A. I can't recall specificconversations.
If
23 occasions demanded that I reach out to the medical group,
24 and if for some reason Papageorge was traveling or
25 unavailable, there were occasions when I would contact
- 61 -
CONCANMOM & JAEGER
WATER PCB-SD0000056501
COMPUTER AIDED TRANSCRIPTION
1 Roush. There would be few occasions when 1 would
2 intentionally roach out rather than through Papageorge if
3 Papageorge was available.
4 Q. {by Mr. Bradley) Do you recall any occasion
5 were you reached out to Dr. Roush and discussed with him
6 information regarding the medical or toxicological aspects
7 of PCBs?
8 A. Mo.
.9 Q, Have you ever spoken with anyone from Nevada
10 Power Company?
11 A. To ray recollection# no.
12 Q, Have- you ever spoken with any salesmen who I
13 have sold the dielectric fluids manufactured by Monsanto to
14 Nevada Power Corapany?
IS HR, FEATHERSTOHE: Any salesman who has sold
16 dielectric fluid manufactured by Monsanto to Nevada Power?
17 HR. BRADLEY: Yes.
18 A. Mo. Because at the point that I became the
19 uielectric manager in 1975# at that particular point in
20 time I believe we had already ceased selling dielectric
21 flui os to anybooy other toan manufacturors oi electrical
I
22 equipment.
23 Q. (by Mr. Bradley) Have you spoken with anyone
24 within Monsanto who claims that they have spoken with
25 anyone from Nevada Power Company?
- 62 -
CONCANNON & JAEGER
~ "WATER- PCB-SD0000056502
COMPUTER AIDED TRANSCRIPTION
1 A. To ray recollection,, no,
*+ Q. Do you know whether PCBs enter the body
3 through the skin? 4 A, We, as a matter of course, for many years in
5 our industrial hygiene made recommendations to users of
6 PCBs, strongly recommended and advocated avoiding prolonged
7 skin contact to preclude any potential entry of PCBs to the
8 system through the skin. There is no question that PCBs
9 have solvency action? we pointed that out. And to the
10 extent that any solvent material can penetrate* the skin,
11 there was a potential of the PCBs to enter the body through
12 the skin.
13 Q. Do you know whether PCBs enter the body
14 tnrough the skin?
15 MR. FEATHERSTORE: Object to the form of the
16 question. 17 Q.
(by Mr. Bradley) I'm not interested in what
18 you told your customers. I'm interested in whether you
19 know whether PCBs enter the body through the skin.
20 A. I don't know that they enter the body through
21 the skin.
22 Q. Have you ever heard the term "furan"?
23 A. Yes.
2 4 Q. Do you know what a fur an is?
25 A. Ye s.
- 63 -
COHCANNON & JAEGER
WATER PCB-SD0000056503
COMPUTER AIDED TRAHSCRIPTIOR
1 Q. What is a fur an? 2 A. It is a cy cl able compound. It1s an organic 3 cy cl able- material. 4 Q. Have you ever heard the terra polychlorinated 5 dibens ofuran? 6 A. Yes. 7 Q. Do you know whether any of the dielectrical 8 fluids manufactured by Monsanto contained any polychlori wr*.' nated dibens ofarans? 10 A. The alleged presence of chlorinated dibenzo11 rurans in chlorinated biphenyls was a claim that came 12 fairly late in the discussions, regulation and control of 13 PCBS. 14 At the time that Monsanto became aware of 15 allegations surrounding chlorinated dibenzoftitans, we again 16 initiated test work within Monsanto to be able for us to 17 verify whether, first, you have the presence, and the test 1 S work, and we concluded that prior to exiting the PCS 19 dielectrics business, as I recall, confirmed only the 20 potential of extremely extraordinary lov? levels of fur ans 21 in higher chlorinated biphenyls that Monsanto had produced. 22 Q, what was your understanding about the levels 23 of the furana in the dielectric fluids manufactured by 24 Monsanto? 25 A. I thought I just answered that question.
-64CONCAMDOM & JAEGER
WATER PCB-SD0000056504
COMPUTER AIDED TRANSCRIPTION
i 0. You did. You said there were extremely small 2 levels. But what were the levels that were found, that you 3 recall? 4 A. In Aroclor 1254f the one report that I saw of 5 work handled in Muir's department, suggested that they may 6 have identified presence in the parts-per-billion level. 7 Q. Have you everheard theterra"ehloracne"? 8 A. Yes. 9 Q. What is it? 10 A. Chi oracne is acondition which was really 11 defined during the Second World War, which was a condition 12 which carried symptoms of skin eruptions, a certain amount 13 of skin darkening, a certain amount of rash, pustules, 14 which was associated at that particular point in time with 15 the use of chlorinated materials, in insulation of cables 16 and certain power control systems in military equipment. 17 Q, Do you know whether there were any reported 18 cases of chioracne prior to the Second World War? 19 A. At the time that people were developing data 20 about the presence of PCBs in the environment and the 21 potential impact of such presence, review was carried out 22 of the previous medical literature concerning chloracne, 23 and, as I recall, there were some earlier reported claims 2 4 of similar symptoms in the thirties and forties, but which 25 subsequent generation of medical information certainly did
- 65 CONCAHHOH S JAEGER
-- -- -- ^cBls^oooogg^og
COMPUTER AIDED TRANSCRIPTION
1 not relate specifically to chlorinated biphenyls. 2 MR. BRADLEY. Read it back, please. 'a*1 (Thereupon, the reporter propounded the previous 4 question.) 3 Q. (by Mr. Bradley) When was the time period 6 that people wore developing data about the presence of RGBs 7 in the environment and the potential impact of such 8 presence that resulted in a review being made of prior 9 cases of chior acne? 10 A. Considerations of the potential presence of 11 ?CB in the environment and the possible impact of such 12 presence, if determined, of any lengthy duration, reached a 13 peak in the period starting from about 1966 and continued 14 until the present. 15 Q. So was there a review made of prior cases of 16 chloracne shortly after 1966 regarding any alleged eorrela~ 17 tic-n be tween chloracne and ? CBs? 18 A. I don't recall when the review of the earlier 19 cases was cone. 20 Q. When did you learn that there had been a 21 review of the earlier cases? 22 A. In the 1974-`75 period. 23 Q. Who told you there had been a review of the 2 4 prior cases of chloracne? 25 ME. FEATHERSTONE? You called it the prior
- 66 CONCANNON & JAEGER
WATER PCB-SD0000056506
COMPUTER AIDED TRANSCRIPTION
1 cases of chi or acne. He called it the literature. Are you o talking about the same thing? Nr. Bradley?
3 HR. BRADLEY: I have ay question out there.
4 It's based upon the notes I have of his testimony. 5 MR. FEATHERSTONEs I object to the form of the
6 question. 7 Q. 8 A.
(by Mr. Bradley) Go ahead. 1 think? given the objection of counsel, we
9 better rephrase the question. 10 Q. Did you not understand the question?
11 A. I*m now confused. 12 HR. BRADLEY; Would you read the last question
13 back? please?
14 (Thereupon? the reporter reaa back a portion of the
15 testimony.)
16 q. (by Mr. Bradley) Who told you chat a review 17 was made of previous medical literature regarding chlor-
1 8 acne?
19 A. It was either Paul Beni gnus or Bill
20 Papage-orge. 21 Q. Did -- Whichever one of them gave you the 22 information? did they indicate to you that a peer-reviewed
23 study had been conducted that discounted the claims made in
24 the 1930s and `40s regarding chloracne and its relationship
2 5 to PCBs?
- 67 -
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WATER PCB-SD0000056507
COMPUTER AIDED TRANSCRIPTION
I A. I an going to have to ask you to repeat that 2 question, because there are a lot of elements in the 3 U *jt X O XI . 4 (Thereupon, the reporter propounded the previous 5 question.) 6 A. Neither one of them claimed a peer review. 7 The information was that a literature review had been 8 carried out which suggested that the symptoms which had 9 been perceived in certain people alleged to be suffering 10 from chi oracne earlier was probably related to exposure to 11 chlorinated napthalenes or other materials other than PCBs. 12 Q. (by Mr. Bradley) Did either Bill Papageorge 13 or Paul Benignus refer you to an article in the Journal of 14 Industrial Hygiene and Toxicology, dated September, 1937, 15 Volume IS, Number 7, by Cecil K, Drinker and others? 16 A. I don*t recall. 17 Q. I* ra going to show you Plaintiff's Exhibit 979 18 and ask you to review that for me. 19 MR. FEATHERSTONE: What do you want him to do? 20 MR. BRADLEY: X want him to review it to 21 indicate to mo whether lie's ever seen it before and whetnor 22 he's familiar with the information in it. So he is going 23 to have to read it. 24 MR. FEATHERSTONE: You want him to read this 9 ^ entire article?
- 68 CONCANNON k JAEGER
WATER PCB-SD0000056508
COMPUTER AIDED TRAMSCRIPTION
1 MR. BRADLEYS Unless he's already seen it fu THE WITNESS; I don't know whether I've seen 3 this article or not. 4 Q. {by Mr. Bradley) In your work at Monsanto 5 have you ever reviewed any articles concerning PCBs that 6 were published in the Journal of Industrial Hygiene and 7 To xioology? 0 A. I don*t recall. 9 Q. Did either Paul Benignus or Bill Papageorge 10 indicate to you that in 1937 a report was written regarding 11 the- effects t rom exposure to vapors of chlorinated 12 diphenyl? 13 A. Either Bill Papageorge or Paul Benignus indi 14 cated that the appropriate people in Monsanto were continu 15 ously reviewing known hygiene effects of PCBs, as we did 16 with all our products. 17 It was not part of ray job. It was not re 18 quired of me or appropriate for me to attempt to encompass 19 the job of all expert functions within Monsanto that helped 20 us to good decision making around the commercialisation of 21 the products that we sold. 22 MR, BRADLEY; I move to strike the answer as 23 nonresponsive. 2 4 My question was whether Bill Papageorge or 25 Paul Benignus indicated to you that in 1937 a study was
- 69 COMCANNON & JAEGER
WATER PCB-SD0000056509
COMPUTER AIDED TRANSCRIPTION
1 done regarding the effects of inhalation of vapor 3 i rora 2 chlorinated diphenyl. 3 A. I don't recall, 4 Q. Have you heard the term,"chlorinated 5 diphenyl '*? 6 A Yes. 7 Q. Is that the same as chlorinated biphenyl? 8 A. Yes.Chlorinated diphenyl is the terminology 9 used in Europe, or chlorinated biphenyl, or the other way 10 around. I mean, there is a distinction across the Atlantic 11 between the use of the terms biphenyl and diphenyl. 12 Q. And are both of them referred to also as PCBs? 13 A. Today, yes. 14 Q. Do you know whether in 1937 anyone usea the 15 term PC3s? 16 A. I have never seen the use of the term PCD at 17 that point in history. 18 Q. When did you know PCB began to be used as a 19 term? 20 A. Probably in the late sixties. 21 Q. And when it began being used as a term in the 22 late sixties, it referred in part, did it not, to what had 23 been referred to as chlorinated diphenyl? 24 A. That was probably not the case until the early 25 seventies.
70 CONCANNON & JAEGER
WATER PCB-SD0000056510
COMPUTER AIDED TRAM SCRIPT ION
1 Q, Dia Bill Papageorge or Paul Benignus ever tell 2 you that in 1937 the effects of ingestion of chlorinated 3 diphenyls were studied? 4 MR. FEATHERSTOMEj Object to the form. 5 A* 1 don't recall. 6 Q. {by Mr. Bradley) Are you familiar with the 7 terra "halowasM? 8 A, I know the term halowax. 9 Q, What was h alow ax in 1937? If you know. 10 HR. FEATHERSTOMEs If you know. 11 A. Yeah. I know the term haiovax was used in 12 relationship to some chlorinated waxy type of products, 13 oeyond that I cannot be more specific. 14 0. (by Mr, Bradley) Do you know whether halowax 15 was comprised in part of chlorinated diphenyl? IS A. Ho, I dorp t. 17 Q. Do you know whether it was comprised in part 18 of chlorinated naphthalene? 19 A. My recollection is that I associate halowax 20 relative to chlorinated paraffins and chlorinated 21 naphthalenes. 22 Q, Do you know whether Monsanto undertook any 23 studies between 1930 and the completion of your work with 2 4 PCD products at Monsanto regarding the health effects of a 25 combination of chlorinated naphthalene and chlorinated
- 71 COMGAMMON & JAEGER
WATER PCB-SD0000056511
COMPUTER AIDED TRANSCRIPTION
1 cU phenyl? o A.
I isave no detailed knowledge of such work.
3 Q. Did Bill Papageorge ever discuss with you any
4 studies that had looked at the effects of exposure to a
5 combination of chlorinated naphthalene and chlorinated
6 diphenyl?
7 A. I do not recall conversations relative to that
8 specific procedure.
9 Q. Do you recall specific conversations relative
10 to that topic with any Monsanto employee?
11 A. ho.
12 Q. Did Bill Papageorge indicate to you that
13 Monsanto knew as early as 1937 that eight or ten General
14 Electric employees exposed to a combination of chlorinated
15 naphthalene and chlorinated diphenyl as part of a halowax
16 mixture wore very severely afflicted, horrible specimens,
17 as far as their skin condition was concerned?
18 MR. PEATHERSTOME: Object to the form.
19 A. As I have already stated, I did not discuss in
20 detail with either Benignus or with Papageorge in any
21 extensive detail work that was relative to the early *>i 4*>* thirties and forties,
23 Q. (by Mr. Bradley) Did anyone ever tell you
2 4 that, if there were a sufficient concentration of PCBs on
2 5 the skin to cause a skin condition or rash, systemic
- 72 -
COM CAM MON c JAEGER
WATER PCB-SD0000056512
COMPUTER AIDED TRANSCRIPTION
1 poisoning may occur in some people who are hypersensitive 2 co PCS s? 3 A. Yes. And that would com the basis for the 4 good industrial hygiene practice which Monsanto communi 5 cated, which was that, if people were working with PCBs and 6 were seen to have any rash or allergic condition, that they 7 should be withdrawn from work in a PCS environment. 8 MR. BRADLEY; I move to strike the answer 9 following the word "Ye3," as nonresponsive and self 10 serving. 11 Did Monsanto ever generate documents informing X1 r>\ readers that exposure to PCBs may cause systemic poisoning? 13 HR. FEATHERSTONE: Object to the form of the 14 Question. 15 A. X don't recall exactly what the cautionary 16 statements of industrial hygiene were in the booklet, the 17 instruction manual. If you have one and want to show it to 18 rae, then 1 could comment to it. 19 Q. (by Mr. Bradley) With your degree in science 20 and with your extensive work history at Monsanto, are you 21 familiar with the phrase "systemic poisoning"? 22 MR, FEATHERSTONE; Can I have the question 4(".i **$J again, please? 24 (Thereupon, the reporter propounded the previous two 25 questions.)
- 73 COMCANNON & JAEGER
WATER PCB-SD0000056513
COMPUTER AIDED TRANSCRIPTION
1 HR. BRADLEY.* Go ahead and answer,
2 THE WITNESS; I was waiting. Did my counsel O want --- Other than listen to those questions, do you want
4 to give me any advice, or -
5 HR. FEATHERSTONEs I've already objected to
6 the form of the question. So, If you can answer it, go
7 ahead. If you can't, tell him that.
8 A. I can't answer it.
9 Q, (by Hr. Bradley) Have you ever heard the term
10 "systemic poisoning"?
11 A. Yes,
12 Q. 3.3 to you?
When you've heard that term, what hasit meant J
14 A. Systemic poisoningis a situation where an
15 exposure at a part of the body does not necessarily create
16 a symptom at that part of the body, but may affect or have
17 an impact on a central system so that symptoms elsewhere in
1 8 the body may then display further additional symptoms.
19 Q. What are the central systems in the body?
20 A, The heart -- Can I answer that question with
21 out it being -- as a generalized thing? I'm not saying
22 that I'm associating in this answer in any way any of these
23 things that might concern the central system where there is
2 4 PCD activity.
25
CONCANHON & JAEGER WATER PCB-SDO000056514
COMPUTER AIDED TRANSCRIPTION
1 A. The heart is a central system/ the lungs are a 0 central system, the liver is a central system,, the kidneys 3 are a central system, 4 Q. Do you know whether any central systems have 5 been shown to be poisoned by exposure to PCBs? 6 A, An exposure to PCBs has been shown to 7 potentially lead to a buildup of PCBs in adipose tissue. 8 Whether that, and when that would proceed to a point that 9 could be defined as poisoning, that gets us into another 10 definition and discussion, 11 Q, Other than the buildup of PCBs in adipose 12 tissue, are you aware of any other central systems that are 13 alleged to have been injured by exposure to PCBs? 14 A. Ho. 15 Q. Has anyone ever indicated to you that liver 16 damage may result from exposure to PCBs? 17 A. The liver is an organ which contains substan 16 tial adipose tissue, and, therefore, buildup of PC3s in the 19 liver area has been associated with PCBs, To the extent 20 that a liver surrounded by adipose tissue containing PCBs 21 may have a change in function, and that the change in 22 function could be considered as damage, then, yes, there is 23 damage * 2 4 Q, Did anyone ever tell you that before March 25 10th, 157C, Monsanto admitted that all customers using
- 75 C0UCA!JN0H jASGER
WATER PCB-SD0000056515
COMPUTER AIDED TRANSCRIPTION
1 dielectric fluids containing PCBs had not been officially ry notified about known effects, nor did Monsanto labels carry 3 information about known effects? 4 MR. FEATHERSTONE: Object to the form. 5 A. Relative to what Monsanto is saying about the 6 usage of PCBs, I have to ask you to divide that question 7 that you just asked me, taking into account and asking me 8 it in terms of, are you asking me about knowledge at the 9 time I was in the sales representative job? or at the time 10 that I was in the European marketing management job, are 11 you asIcing 12 MR. FEATHERSTOWEs I think the question is 13 narrower than that. I think the question is whether any 14 body has ever admitted to you, whatever the question, and IS then goes on to state. Why don1t you ask to have the ques 16 tion repeated. 17 (Thereupon, the reporter propounded the previous 18 question.} 19 A. No. 20 MR. BRADLEY? Off the record for just a 21 moment. 22 (Thereupon, a luncheon recess was taken.) 23 Q. (by Mr. Bradley) During the period of time in 2 4 the 1960s when you were working with dielectric fluids '? 8 containing PCBs, aid you relay any information to any
"76COMCAMMOM & JAEGER
WATER PCB-SD0000056516
COMPUTER AIDED TRANSCRXPTION
1 electrical utility industry group regarding the effects of 2 exposure to PC3s? 3 A. At the time that I was involved with PCS 4 dielectrics in the sixties, there would be occasions when X 5 would talk to utilities that used the electrical equipment 6 about the handling and maintenance of the equipment. I can 7 recollect a few occasions when that sort of communication 8 occurred during that period. Q Q. During the 1960s did you talk with any 10 electric utility companies within the United States regard" 11 iny the effects of FCBs? 12 A. No, I did not. 13 Q. During the 1960s were you aware of any 14 communications Monsanto Company .made to electrical utility 15 companies within the United States regarding the effects of 16 expsure to PCB s ? 17 h. Only to the extent that such coram uni cations 18 were translated into instruction manuals that would be 19 supplied to European users of our materials. 20 Q. What work cUd you do when you were no longer 21 manager of dielectric fluids? What was your next job 22 title? 23 A. Arc we now in the late seventies period? 24 Q. That* s my understanding. 25 A. Immediately after I was manager of
- 77 ~ CON CANNON & JAEGER
WATER PCB-SD0000056517
COMPUTER AIDED TRANSCRIPTION
1 dielectrics, I was manager of heat transfer fluids. 2 Q. Over what period of time were you the manager o or heat transfer fluids? 4 A. That was about a two-to-three-year period. 5 Q. Beginning when, roughly? 6 A. * 76, '77. 7 Q. Okay. During your work as manager of heat 8 transfer fluids, did you have any involvement with PCBs? 9 A. Yes, I did. 10 Q. And what was that involvement? 11 A. To the esteat that there were residual 12 correspondence questions, issues after we had stopped 13 manufacturing and distributing and selling PCB-containiny 14 dielectric fluids, I was called upon occasionally to handle 15 questions outside of Monsanto which pertained to the time 16 that wo had been in that business. 17 Q. Were those questionsposed from electrical 18 utility companies? 19 A. 1 believe I may have had a limited number of 20 isolated questions from utility companies during that 21 period of time. 22 Q. I take it, though, that the heat transfer 23 fluids that you were managing did not contain PCBs? 24 A. They did not. 25 Q. What was your nextjob title?
-78COUCkimOU JAEGER
WATER PCB-SD0000056518
COMPUTER AIDED TRAMSCRIFTIOH
1 A. Manager of rav/ material pur chases.
2 Q. end?
When did you begin that job and when did it
4 A. It began in the period or either 1979 or * 80,
5 and it would have ended in 1982.
6 Q. What was your next job title?
7 A. I became commercial director for Monsanto
8 Ch era ical Com pa ny in Bras il.
9 Q. When did you begin and end that job?
10 End of March of 1982, and 1 finished it in
11 September of 1988.
12 Q, What was your next job title?
13 A. I then became business director for plasti
14 cisers ana specialty resins.
15 Q. When did that job begin? 16 A. That job began in September of 1988.
17 Q, When did it end?
X o A. Until sometime in 1989.
IS Q. What was your next job title? 20 A. Business director for polymer modifiers in the
21 specialties division.
22 Q. Did that begin in 1989? 23 A Yes.
2 4 Q, And when did it end?
25 A. That job ended in 1991.
- 79 -
COMCAMKOH A JAEGER
WATER PCB-SD0000056519
COHPUTER AIDSD TRANSCRIPTION
1 Q, Wnat was your nest job title? 2 A. Business director , Safi ex Americas, S-a-3 l-e~x, Americas, with an S on the end. 4 Q. What is Safiex Americas? S Q, Safi ex is a plastic sheet which is used to 6 laminate glass in such applications as safety in automotive 7 windshields. Every windshield in the western world con 8 tains a plastic laminate to protect passengers. It is all 9 plastic, and Monsanto is the major V70rld producer of that 10 plastic sheet. 11 Q. Over what period of time were you director of 12 Saflex Americas? 13 A. From 1991 until the present time. Americas 14 implies that X have responsibility for that particular 13 business in North and South America. 16 Q. Were you -- Lot me ask it this way* Do you 17 know whether Monsanto and its customers have entered into 10 indemnification agreements regarding the customer sale of 19 PCBS? 20 A. In the early 1970s, before I became responsi 21 ble for the dielectric business in the Americas -- North 22 America, Monsanto had entered into agreements with our 23 customers who produced dielectric equipments in which they, 24 to a certain extent, indemnified Monsanto against the con 25 sequences of their mishandling our PCBs.
-80CONCANHOH & JAEGER
WATER PCEbSDO000056520
COMPUTER AIDED TRANSCRIPTION
1 Q. Do you know whether Monsanto* s customers' 2 customers were informed of the indemnification agreement 3 that you just discussed? 4 A, No. 5 Q. Monsanto sold dielectric fluid beginning in 6 the 1930s? is that -- Let me rephrase the question. 7 Monsanto sold dielectric fluid containing PCBs 6 beginning in the 1930s? is that correct? 9 A. My recollection of the historical perspectives 10 that I was given when 1 became involved with the business II is that we entered that business sometime in the 1930s. 12 Q. Do you know whether Monsanto customers were 13 ever informed regarding the 1930s studies that associated 14 chioracne with exposure to chlorinated diphenyl? 15 HR. FEATHERSTONE; Object to the form. 16 A. At the time that 1 became involved with 17 dielectric fluids containing PCBs. I know that our instruc 18 tion manuals which were supplied to producers of electrical 19 equipment containing such fluids certainly contained 20 industrial hygiene recommendations which recognised that 21 skin contact for a prolonged period was undesirable. 22 Beyond that it would be pure speculation on my part. 23 Q. Do you know whether Monsanto ever informed its 2 4 customer s that chi oracne was a condition known in the 25 thirties to be caused by exposure to a mixture of
- 81 CONCANMON & JAEGER
'' "
' ' ~WATER PCB^SD000b056521
COMPUTER AIDED TRANSCRIPTION
i chlorinated naphthalene and chlorinated diphenyl? 2 A, I do not have specific knowledge about that. 3 Q, Do you know whether Monsanto ever informed its 4 customers that pathologic changes in animals exposed to a 5 commercially chlorinated diphenyl were reported as early as 6 1944? 7 A. No. 8 Q. Bo you know whether Monsanto ever informed its 9 customers that the toxicity of the vapors of Aroclor 1242 10 and 1254 were documented as early as 1956? .11 A. Ho. 12 Q. Do you know whether Monsanto ever reported to 13 its customers that ninety-nine percent of all Americans 14 reportedly have over five hundred parts per billion PCBs in 15 their adipose tissue? 1G A. Could you repeat the question? 17 0. Do you know whether Monsanto over informed its 10 customers that ninety-nine percent of all Americans 19 reportedly have over five hundred parts per billion PCBs in 20 there adipose tissue? 21 MR, FEATHERSTONE5 Parts per billion? Is that 22 what you said? 23 MR. BRADLEYS Yes. 2 4 A, I don't believe Monsanto ever carried out any 25 work which would have caused us to make such an estimate
- 82 COW CAM WOE & JAEGER
WATER PCB-SD0000056522
COMPUTER AIDED TRANSCRIPTION
1 tor us to communicate to our customers. There were 2 allegations that PCBs were broadly present in the adipose 3 tissue of the population of America* but, in that it was 4 not for us to fuel nonscientific speculation by reporting 5 every allegation that was made at that time, we probably 6 did not report such. 7 Q. (by Mr. Bradley) Are you familiar with the 8 tend biomagnification? 9 A. Yes. 10 0. What is it? 11 A. Bioiaagnification is the process by which a 12 material can be assimilated by a species in the ecological 13 chain, and as that particular species, as a natural food 14 for a higher species, is consumed, then the presence of the 15 material that may be in the adipose tissue of the consumed 16 species is magnified in the tissue of the consuming 17 species. 1 8 Q* Are you familiar with the phrase food chain? 19 A. Yes. 20 Q. Do PCBs biomagnify in the human food chain? 21 A. Yes, they can. 22 Q. Did Monsanto ever inform its customers that 23 PCBs can biomagnify in the human food chain? 24 A. Yes, we did. 25 Q. And how did you do that?
- 83 CONCANNON & JAEGER
WATER PCB-SD0000056523
COFPUTER A1DED TRAMSCRIPT10N
1 A. As part of the notification to our customers 2 of the need to avoid contaminating waters with PCBs. lie 3 used examples, as I recall, of biomagnification in the fish 4 food chain. 5 Q. Where would that information have been?
6 MR. FEATHERSTORE: I* ra sorry. Where would
7 that information have been?
G Q. (by Mr. Bradley) Is that in the instruction
9 manual?
10 A. Ho.
11 Q. Where was it iocatea?
12 MR. FEATHERSTONE? You mean, in what form was
13 it communicated?
14
Q.
(by Mr. Bradley) Thankyou.
In what form was
15 it communicated? 16 A. As Monsanto over a period of time developed 17 information about the fate of PCBs in the environment, we lb kept our customers aware on a continuing ongoing basis of 19 various studies that were carried out which related to 2 0 distribution of PCBs in the environment, and -- 21 MR. FEATHERSTONE: I think he's asking you 22 whether it was done in a written fora or whether it was 23 done in meetings. How was that information communicated? 24 Q. (by Mr. Bradley) Brochures, letters, 25 instruction manuals?
- 84 -
COMCANNON & JAEGER
WATER PCB-SD0000056524
COMPUTER AIDED TRADSCRIPTION
1 A. Letters and discussions. 2 Q. Did you ever author a letter to a customer -- 3 Before I -- Let me stop that question for a moment and ask 4 to have the last question read back. 5 {Thereupon, the reporter propounded a portion of the 6 testimony.) 7 Q. (by Mr. Bradley) Let rae start a new questions 8 Mr. Wood, did you author any letters to any Monsanto custo 9 mers informing those customers that PCBs can biomagnify in lG- the human food chain? 11 h. Almost certain!y not. 12 Q. Did you ever rev lev; any letter authored by a 13 Monsanto employee which Informed Monsanto customers that 14 PCBs can biomagnify in the human food chain? 15 A. I believe, yes. 16 Q. Who authored that -- Who were the authors, if 17 there was more than one, of those letters, if there was ie more than one? 19 A. That type of communication would probably have 20 been authored by Jim Muir, Bill Papageorge. These are the 21 names that come to mind as people who would compose such 22 letters. 23 Q. I'm interested in knowing whether you surmise 24 that these gentlemen wrote those letters or whether you '"t f" ever remember reviewing a letter written by anyone that
- 85 COMC&HMQM & JAEGER
._
WATER- PCB^SDO000056525
COMPUTER AIDED
SCRIPT ION
1 informed Monsanto customers that PCBs can blorasgnify in the
& human food chain.
3 A. I know that there were questions from our
4 customers about the issues of biomagnifieation, and? there
5 fore, I know tnat individual letters would have been
6 authored by such people In response to such questions. I
7 am not aware of any general open customer letter
8 communication that they authored.
9 Q. And going bade for a moment, do you recall
10 ever rev levying a letter written by a Monsanto employee to
11 Monsanto customers that discusses PCS biomagnification in
12 the human food chain?
13 A. I don't recall that.
14 Q. Did you have any discussions with any Monsanto
15 customers where Monsanto informed the customers that PCBs
16 can biomagnify in the human food chain?
17 A. Yes, I did.
18 Q. When did those occur?
19 A. Between 1973, January, and 1976, `77.
20 Q. With whom did you have those discussions? 21 A, At various points I would have had discussions 2 2 around those subjects with every one of our U.S. customers.
2 3 Q. So you had those discussions with General
2 4 Electric? 25 A
Yes.
- 86 -
CON CAN II ON & JAEGER
WATER PCB-SD0000056526
COMPUTER AIDED TRANSCRIPTION
1 Q. And you had those discussions with 2 Westinghouse? 3 A. Yes, 1 did. 4 Q. Do you knowwhether anyonewithinMonsanto 5 prior to 1975 informed its customers that PCBs can 6 biomagnify in the human food chain? 7 A. 1 surmise that they musthave done because S Dioiaagnification was not an alien term in discussions 9 between Monsanto and its customers when I became involved 10 in this business in 1975. 11 Q. nave you ever reviewed a letter written by any 12 of Monsanto's customers to their customers that indicates 13 that. PCBs can biomagnify in the human food chain? 14 A. Mo. .15 w Have any of Monsanto's customers ever informed 16 you that they have told their customers that PCBs can 17 biomagnify in the human food chain? 1 8 MR. FEATHERSTOME; I think we're on Monsanto's 19 customers to its customers. Is that right? 20 THE WITHESS: I thought we had just departed 21 from that. 22 MR. FEATHERSTONE; Well, let's have the ques 23 tion back, then, to prevent any confusion on this. 2 4 (Thereupon, the reporter propounded the previous 25 question.}
- 07 CONCANNON & JAEGER
WATER PCB-SD0000056527
COMPUTER AIDED TRANSCRIPTION
1 A. Monsanto* a customers advised me that they were 2 communicating with their customers about the presence and 3 impact of PCB in the environment. Whether they specifical4 iy in such communi cation dealt with biomagnification, I 3 cannot with certainty say, 6 Q. (by Mr. Bradley) Do you know what the terra 7 "synergisa" means? 8 A. Yes. 9 Q. What does synergism mean? 10 A. Synergism means that a particular activity 11 related with fcv/o or more individual products can be 12 magnified more than by purely the additive affect of those 13 two activities when they are combined. 14 Q. Can PCBa work synergistleally with other 15 compounds impairing an immune system? 16 HR. PERTHHRSTORES Objection. Calls for 17 speculation on this witness' a part, 1 8 A. I have no knowledge, 19 Q. {by Mr. Bradley) Do you know whether Monsanto 20 ever informed its customers that PCBs can work syner21 gisticaily with other compounds by impairing the immune 22 system? 23 A. Ho. 24 Q. Ho, you don*t know, or no, Monsanto didn't 25 relay that information to its customers?
- 88 CONCANNON 6 JAEGER
WATER PCB-SD0000056528
COMPUTER AIDED TRANSCRIPTION
1 A. You asked rue if 1 knew if Monsanto had ever, 2 and I said no. 3 Q. Did Westinghouse- ever inform you that it knew 4 as of 1938 that PCS contact with the skin can cause 5 systemic effects, including injurious effects to the liver? 6 A. Westinghouse never told me this. 7 Q. Did General Electric ever tell you that it 8 knew in 193 8that PCB contact with the skin can cause 9 systemic effects, including injurious effects on the liver? 10 A. General Electric never told me this. 11 MR. FEATHERSTORE: Could I have that last 12 question back? 13 (Thereupon, the reporter read back the question.} 14 A. In both cases, in answer to both of those 15 questions, I was never told that by Weatinghouse and I was IS never tola that by General Electric. 17 Q. (by Hr. Bradley) Dici Westinghouse ever tell 18 you that itknew in 1947 that chronic poisoning nay occur 19 with repeated exposures to sufficient concentrations of PCB 20 vapor ? 21 A. No, 22 Q. Did General Electric ever inform you that in 23 1947 it knew that chronic poisoning may occur with repeated 24 exposures to sufficient concentrations of PCB vapor? 23
COM CANNON & JAEGER WATER PCB-SD0000056529
COMPUTER AIDED TRANSCRIPTIOK
1 Q. Did Monsanto inform its customers prior to 2 1970 that chronic poisoning may occur with repeated 3 exposures to sufficient concentrations of PCB vapor? 4 MR. PEATEIERSTONEj 11m sorry* Let me hear the 5 first part of that question back* 6 (Thereupon, the reporter propounded a part of the 7 previous question.) OO MR. FEATHERSTORE! All right. That's all I 9 need, 10 (Thereupon, the reporter propounded the previous 11 question in its entirety.) 12 MR. FEATHERSTONE: I object to the form of the 13 question as calling for speculation on the part of the 14 witness as to what may have happened at Monsanto prior to 15 1970. No foundation for him to answer the question on 15 Dehalf of the entire company. 17 A. I certainly made no such disclosure to ray 18 customer base in Europe. 19 q. (by Mr, Bradley) Were you ever provided any 20 documents in the work that you did with Monsanto that 21 indicated Monsanto knew in 1947 that chronic poisoning may 22 occur with repeated exposures to sufficient concentrations 23 of PCB vapor? 24 A. No. 25 Q. Were you ever informed during your work at
- 90 CONCANNON & JAEGER
WATER PCB-SD0000056530
COMPOSER AIDED TRANSCRIPTION
1 Monsanto that repeated exposures to PCS vapor may produce 2 internal bouily injury which may be disabling or could be 3 r staj.? 4 A, Sorry* It's just the fora -- the form of 5 ingestion I didn* t capture in that question. 6 MR. BRADLEY: Would you read the question 7 back? 8 (Thereupon, the reporter read back the question.) sCi A. I was informed by Monsanto that exposure to 10 vapors of PCBs at high levels at high temperatures should 11 be avoided. This was never communicated to me in a sense 12 that this was potentially fatal. 13 Q, (by Mr. Bradley) Did Monsanto ever inform its 14 customers that periodic physical examinations should be 15 conducted by medical personnel for workers exposed to PCBs? 15 MR. FEATHERSTOME: Object to the form of the 17 question and to the absence of foundation for this witness 18 to testify on behalf of Monsanto over a long period of 19 time. Calls for speculation. 20 A. The standard industrial hygiene practice that 21 was communicated in our instructional manuals to dielectric 22 users did not include recommendation as to routine medical 23 inspection. 24 Q. (by Mr, Bradley) And over what period of 25 years are you familiar with those instruction manuals?
- SI C0NCAKH0H & JAEGER
WATER PCB-SD0000056531
COMPUTER AIDED TRANSCRIPTION
1 h An initial period between 1965 and 1970, and a 2 secondary phase between 1975 and 1978. 3 Q. Did you ever review instruction manuals 4 prepared prior to 1965? 5 A. No, I did not. 6 Q. Have you ever heard of Congressman Ryan? 7 A. I recall the name. I can* t recall in what 8 contest I know the name. 9 Q. Do you know whether Congressman Ryan in 1970 10 proposed legislation that would impact upon the sale of 11 PCBs? 12 A, No.
.)
13 Q. Do you know whether in 1955 Monsanto knew that 14 production workers manufacturing PCBs experienced chlorIS acne, gastric troubles, and liver troubles? 16 Let me rephrase the question. I'm not happy 17 with that question. Do you know, during the period of time 1 0 you were employed at Monsanto, whether it ever informed its 19 customers that it was reported in 1955 that production 20 workers manufacturing PCBs experienced chloracne, gastric 21 troubles, and liver troubles? 22 HR. FEATHERSTONE: Object to the form of the 23 question. 24 MR. BRADLEY; what's wrong with the form of 25 the question?
~ 92 COWCANNON k JAEGER
WATER PCB-SD0000056532
COMPUTER AIDED TRAM SCRIPT 1023
1 HR. FEATHERSTONEs It misstates the evidence. 2 Q. {by Hr. Bradley) Go ahead and answer.
3 A. I`m unable to respond to that question. I
4 have no knowledge of such communications prior to my being
5 involved, and certainly 1 was not involved whilst I was
6 responsible with any such comiaunicat!on.
7 Q, You* re familiar v?ith the work of Professor
8 Widmark?
9 A. Professor widraark, to my knowledge, did very
10 little work himself with any relevance to the subject we're
11 talking about.
12 g. Are youfamiliar with thework of Dr.Jensen?
13 A, Yes.
14 Q. Did he issue a published report in 1967
15 regarding PCBs in the environment?
16 A. NO. 17 Q. When did he issue a report? If he did.
18 A. I believe hisreport, which he commented about
IS the work earlier, but his report was issued no earlier than
20 1969. 21 Q.
Was his report a published report?
22 A. Which one are we talking about? 23 Q. The one in *69, I guess, 2 4 A. 1 believe his work was finally presented in a
25 published form sometime in the 1969 time frame,
- 93 -
CON GANN ON & J AEG ER
WATER PCB-SD0000056533
COMPUTER AIDED TRANSCRIPTION
i Q. &r> to *68?
Has it available in an unpublished form prior
3 A. It had been -- Commentary about the direction
4 that his work was taking were released by Dr. Jensen and
5 Dr. Widmark in the winter of 1966.
6 Q. What was Dr. Jensen reporting?
7 A. I don't believe Jensen was a doctor at that
8 time, so that Dr. Jensen, he was not a doctor reporting
9 anything at that point in time.
10 Q. What was Mr. Jensen reporting?
11 MR. PE ATII EH S TO U E: Object to the form.
12
Q, (by Mr. Bradley) What was
Mr. Jensen
13 reporting in this unpublished study that came out in 1966?
14 MR. FEATHERSTONE: Wait a minute. The witness
15 has tal Ice ci a bout commentaries in the winter of 1966. Is
16 that what you're talking about?
17 MR. DRADLEYs The witness has talked about a
18 published study that appeared in *69 and commentaries that
19 were are released in the winter of *66. That's what my
20 notes show*.
21 Were the commentaries written by Mr. Jensen or
22 oy others?
23 A. By others.
24
Q. (by Mr. Bradley) Here the
commentaries
25 comments on an unpublished study prepared by Mr. Jensen?
- 94 -
COMGAMMON & JAEGER
WATER PCB-SD0000056534
COMPUTER AIDED TRANSCRIPTION
1 A. The commentaries departed from art unpublished 2 stuay of work in progress by Mr. Jensen and extended themTM
selves into areas of speculation which were of some 4 embarrassment to Mr. Jensen. 5 MR. BRADLEY: I move to strike the answer as G nonresponsive. 7 Here the commentaries evaluations of an un~ e published work that was being circulated by Hr. Jensen? 9 A. Mo. Certainly not. 10 Q. (by Mr. Bradley) All right. What were -- 11 Were the commentaries on -- Well, let me ask it this ways 12 What were the commentaries commenting on? 13 A. Commentaries in December of 1966, based on 14 some analytical studies which Hr. Jensen was conducting but 15 had not completed, were made essentially at the instigation 16 of people who were manufacturing an analytical -- a piece 17 of analytical equipment which they wished to promote at 18 that particular time. 19 The press releases about the performance of 20 that equipment related to the ability of such equipment to 21 determine the presence of the environmental contaminants of 22 a chlorinated nature in the environment. The commentary 23 related to some things or the presence of some molecules 2 4 other than BDT, which the particular study was involved 25 with, and beyond that point, the rest of the commentary was
" 95 COHCAIINOH 6 JAEGER
WATER PCB-SD0000056535
COMPUTER AIDED TRANSCRIPTION
1 spacuiative. 2 Q. Was there any discussion in the commentaries 3 of PCBS? 4 A* No. There was a commentary at that point in. 5 time about some -materials which were described by the 6 commentators as chlorinated diphenols. And this created 7 some major confusion as to what chlorinated species of 8 industrial or agricultural product was Jensen really 9 addressing in ais analytical study. 10 Q. Was there a tine when it was made clear that 11 chlorinated diphenols were chlorinated diphenyls? 12 MR* PBATHERSTONE: Wait a minute. That 13 doesn't foliov/. You mean that that's what he was talking 14 about ? 15 MR. BRADLEYs Yes. Chlorinated diphenols# and 16 in fact, he was talking about chlorinated diphenyls. 17 Can you answer the question? 18 A. Sure. ID MR. PE AT HERS TO M E s Then go ahead and answer 20 it. 21 A, To my mind, the query as to what chlorinated 22 species really were involved in Mr. Jensen's study, to my 23 mind, was not scientifically resolved until about 1969 or 24 even later. 25 Q. (by Mr. Bradley) When it was scientifically
- 96 CONCANNON & JAEGER
WATER PCB-SD0000056536
COMPUTER AIDED TRAM SCRIPT IOI3
1 resolved,, what chlorinated compound was it that was 2 involved in Mr. Jensen's study? 3 A. Highly chlorinated biphenyls. PCPs, as they 4 became known. 5 MR. FEATHERSTOKEs When you said "chlorinated 6 diphenols," would you spell that for the reporter? 7 THE WITNESS: Yes. The original Swedish 8 language articles commenting on Jensen talk about work 9 related to a chemical material described as chlorinated 10 diphenols, d-i-p-h-e-n-o-l-s. 11 MR. F2ATHERST0NE: All right. 12 0. (by Mr. Bradley) Okay. And how is that 13 different from the spelling of chlorinated diphenyls? 14 A. A phenol radical is a bens one ring with a 13 hydroxyl group associated with it. 15 0. I'm just talking about the spelling? How does 17 the spelling differ? 18 A. Diphenyl has a Y in place of the O, but 19 they're very different chemical materials, and, therefore, 20 whether my answer is self-serving or not, we have to be 21 very precise on what we're talking about. 22 MR. BRADLEY: I move to strike as nonrespon23 sive. 24 MR. FEATHERSTONE: Off the record. 2 5 (Thereupon, a short colloquy was had.)
- 97 COHCANNOH & JAEGER
WATER PCB-SD0000056537
COMPUTER AIDED TRANSCRIPTION
1 Q. (by fir. Bradley) And at the time of the 2 Jensen published report in 1969, was he a doctor? 3 A. 1 don't know. I don* t know whether he 4 received his doctorate or not. 5 Q. And following his report, do you know whether 6 Monsanto increased or decreased its production of PCBs? 7 HR. FEATHERSTONE! Which report, now? 8 MR. BRADLEYs The 1969 published report. 9 A. Chronologically, Monsanto"e reduction of its 10 output of PCBs was after the publication of the Jenson 11 report, but I must insist that that is purely that. I 12 mean, cnronologically vie reduced production, in time, after 13 the publication of Jensen's report. 14 Q. (by Mr. Bradley) Well, let me ask this ques 15 tion: Did you increase or decrease the production of PCBs 16 In 1970 versus 1969? 17 A. On a worldwide basis, I do not have that know 1 8 ledge . 19 Q. How about on the -- using the United states as 20 a universe? Between 1969 and 1970, did Monsanto increase 21 or decrease its United States production of PCBs? 22 A. I don"t know. 23 Q. Between 1969 and 1971, did Monsanto increase 24 or decrease its worldwide product ion of PCBs? 23 A. I don* t know.
- 98 COMCAMMOM & JAEGER
WATER PCB-SD0000056538
COMPUTER AIDED TRANSCRIPTION
1 Q. Can you tell me what year Monsanto first 2 reduced its worldwide production of PC3s following issuance 3 of the published report by Jensen in 1969? 4 MR. FEATHER3T0NE: Object to the form of the 5 question. Also calls for speculation on the part of the 6 witness, since he's already told you for several of those 7 years he doesn't know one way or the other. 8 Q, (by Mr. Bradley) Mr. Mood, if you don't know 9 the answer, just tell me you don't know it; if you do know 10 the answer, go ahead and answer it. 11 A. Because 1 was uninvolved with PCBs during that 12 period, I don't know the answer to that question. 13 Q. Ail right. Do you know what it means to bio 14 degrade? 15 A, Yes, I do. 16 Q. Do PCBs manufactured by Monsanto biodegrade? 17 A, Yes. 18 Q. What does biodegrade mean? 19 A. Biodegrade means that when a chemical is 20 present in the environment in contact with other naturally21 occurring species in the environment, that the material 22 will gradually be broken down into smaller components. 23 Q. And if a compoundbreaks down into smaller 24 components but does not completely disappear, does it still 23 Diodegrade?
COWCANNON & JAEGER WATER PCB-SD0000056539
COMPUTER AIDED TRAHSCRIPT 1013
1 A. Yes. 2 Q. And how is that expressed, as complete bio 3 degradation, partial biodegradation, or some other phrase 4 or term? 5 MR. FEATBERSTOHEi Object to the form of the 6 question. 7 Q. (by fir. Bradley) What phrase is used to refer 8 to a compound that breaks down into smaller components but 9 docs not completely disappear? 10 A. I would refer to it as a partially biodegrad 11 able mixture. 12 Q. Are the PCBs manufactured byMonsanto com 13 pletely biodegradable or partially biodegradable? 14 A. Partially biodegradable. 15 Q. Are there any PCBs manufactured byMonsanto 16 that are completely biodegradable? Excuse rae. Let me 17 rephrase that. During the period of time that you were 1 O working with Monsanto relative to the issue of PCBs, were 19 any of the PCBs manufactured by Monsanto completely bio 20 degradable? 21 MR. FEATHERSTOME * Are you talking about 22 product mixtures, or are you talking about individual 23 isomers? 24 MR. BRADLEY % 1 understand, you know, from the 25 Tucker deposition that there is a difference. 1 want to
- 100 COHCAHROn & JAEGER
WATER PCB-SD0000056540
COMPUTER AIDED TRAN SCRIPT 1012
1 hear what his understanding is and explanation of it, so 2 I'ra just going to leave the question as it is. 3 MR. FEATHERSTOME: Object to the form of the 4 question. 5 A. polychlorinated biphenyls, as sold by Monsanto 6 for various dielectric applications, were coraplex mixtures 7 of Isomer3. The various isoraers of chlorinated biphenyl 8 have differing biodegradation rates, and those varying 9 biodegradation rates will themselves vary depending on the 10 environment within which the biodegradation is occurring, 11 So discussion about complete or incomplete biodegradation 12 can only be discussed relative to specific PCB mixtures and
.}
13 different specific environmental exposures, 14 Q. (by Hr, Bradley) During the time you were 13 working with PC3s at Monsanto, were there any PCD mixtures 16 that completely biodegraded? 17 A. Certain isomers of polychlorinated biphenyl in 18 tests carried out by Monsanto were shown to biodegrade com 19 pletely. 20 Q. Were any tests conducted by Monsanto outside 21 of a laboratory situation which showed that -- Strike the 22 question. 23 Would you read back his answer to me? 24 (Thereupon, the reporter propounded the previous 25 answer.)
- 101 CONCANNON & JAEGER
____
_ WAT EfT PCB-SD0000056541
COMPUTER AIDED TRANSCRIPTION
1 Q. (by Mr. Bradley) Did Monsanto perform any 2 test to determine whether the isomers which were shown to 3 biodegrade completely would biodegrade completely outside 4 of the laboratory? 5 MR. FEATHERSTOHE: Object to the form. 6 A. That would not have been a fruitful lino of 7 testing, so we did not. 8 Q. (by Mr. Bradley) I have shown you Plaintiff's 9 Exhibit 424 ju3t before vie started up again following the 10 lunch hour. Is that an exhibit you have ever seen before? 11 A. You said 424. 12 Q. Let me start the question again. 1`m now 13 showing you Plaintiff's Exhibit 422 which I asked you to 14 review just before we started up again here following our 15 lunch break. Is that an exhibit that you have seen prior 16 to today? 17 A. Ho, I haven' t. 16 0. Okay. I'm going to show you Plaintiff's 19 Exhibit 435 and ask you to rev lev/ that for me, please. 20 A. Yes. 21 Q. Is this a letter written by you? 22 A. Yes, it is. 23 Q. All right. And it's to George Buchanan in St. 24 Louis? 25 A. Yes, it is.
- 102 CONCAMNOW & JAEGER
WATER PCB-SD0000056542
COMPUTER AIDED TRANSCRIPTION
1 Q. And it* s dated December 1, 1966? 2 A. Yes, it is. 3 Q. And attached to the letter is a copy of a 4 letter received from Ola Palm in Stockholm? 5 A. The signature appears to be "Ola,H and given 6 my knowledge of the -- or remembrance of the organisation, 7 that would have been Ola Palm. 8 Q. And is this exhibit a true and accurate copy 9 of the letter you authored December 1, 1966 to George 10 Buchanan with the attachment? 11 MR. FEATHERSTONE: Are you excluding the hand12 wri ting that's on the second and thira pages? 13 Q. (by Mr. Bradley) Let me first ask: Is that 14 your handwriting on the letter from Ola Palm to you? 13 A. No. IS MR. FEATHERSTONE: Let's go off the record. 17 {Thereupon, a discussion was had.) 10 Q. (by Mr. Bradley) Other than the handwriting 19 on the first page of the letter written to you by Ola Palm, 20 is this a true and accurate copy of the letter you wrote 21 December 1, 1966 to George Buchanan attaching the letter 22 directed to you from Ola Palm in Stockholm? 23 A. The copy of the letter from Rising & strand is 2 4 indeed a copy of the letter I received from them. The 23 letter dated the 1st of December is my letter to George
- 103 COUCANNON & JAEGER
.-
WATER PCB^SD0000056543
COMPUTER AIDED TRANSCRIPTION
Buchanan. Other than the handwritten notes on the Rising &
2 Strand letter, there are some under!inings of emphasis on
3 page two and some aide-linings on page three which are not
4 mine. 5 Q.
Otherwise, it's a true and accurate copy?
6 A. Yes, it is.
7 Q. Did you write the letter to George Buchanan,
8 December 1, 1966, shortly after you received the letter
9 front Ola Palm in Stockholm?
10 A. Given the normal mail transmission time, the
11 Rising & Strand letter you see is dated November 28th, and
12 almost immediately I wrote to Mr. Buchanan.
13 , Is this a document that you maintained in your
14 files at Monsanto as part of Monsanto1s regularly-conducted
15 business activity? 16 A. It would normally have been in my dielectric
17 Sweden file.
18 Q. Okay.
IB MR. FEATHERSTONE: About that question, Hr.
20 Bradley, you were intending to ask him about his copy of
21 the letter without somebody else's handwritten marginal
22 notes?
23 MR. BRADLEY: That's correct. Without the
24 handwritten notes and without the underlinings arid without 25 the lines drawn beside two paragraphs on the last page from
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1 01 a pal si. 2
MR, PE ATHERS TOM E s Okay.
3 Q. (by Hr. Bradley) Mr. Wood, I have shown you
4 Plaintiff's Exhibit 358. Is that a memorandum that you
5 wrote to Bill Papageorge on October 30th, 19757
6 A, The heading would suggest so.
7 Q. All right. Is this a true and accurate copy
8 of the letter that you wrote to Mr. Papageorge on that
9 date?
10 A. I don't recall every letter I wrote in 1975.
11 It does not seen to have been tampered with.
12 Q. And is this a document you wrote regarding
13 an SPA letter received October 17, 1975?
14 A, That's what the reference to this memo
15 suggests.
16 Q. Is this a document that you kept in your files
17 at Monsanto as part of its regularly-conducted business?
18 A. Yes.
19 Q. I'm now going to show youPlaintiff's Exhibit
20 357 and ask you to review that document.
21 Let's go off the record for a moment.
22 (Thereupon, a short recess was taken.)
23 Q. (by Mr. Bradley) Mr. Wood, youhave before
24 you both Plaintiff's Exhibits 357 and 358?
25 A. Yes.
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Q Exhibit 358, which we have previously spoken r&-\ about, indicates that it's a comment on an EPA letter
3 received 10-17-1975. Is Plaintiff's Exhibit 337 the letter 4 from the EPA that is referenced in Exhibit 358?
3 A. Yes.
6 Q. Is that a true and accurate copy of the letter
7 that is referred to in Plaintiff's Exhibit 358, absent the
8 markings and handwriting? 9 A. Are we on 358 or 357? 10 Q. Let me start all overagain.
On 357 there are
11 some underlinings and there are some handwritten words.
12 A. Yes, there are. 13 Q. Did you write those handwritten words? 14 A. Yes.
15 Q. Did you underline thoseportions ofExhibit 16 357 that are underlined?
17 A. Yes.
18 Q. And did you put the markings next to certain
19 paragraphs, the straight line up and dawn?
20 A. Yes. 21 Q. And is this a true andaccurate copy of the
22 letter that you received October 17, 1975 from the United
23 States Environmental Protection Agency?
24 A. Yes. 25 Q. is this adocument that youmaintainedwithin
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1 your files at Monsanto as part of Monsanto's regularly2 conducted business? " A. Yes. 4 Q. Turning to 3 58, on the second page under it era 5 twelve, you have listed Q10, which I assume means question 6 ten. It says, None, question mark; Yusho, question nark; 7 Cloracne years ago, hyphen, Dangerous Question. What were 8 you referring to when you indicated there was a dangerous S question? 10 A. Question ten in the EPA letter requests a 11 description of any adverse health or environmental effects 12 which you know or believe speculate to have resulted from 13 the introduction of PCB compounds. 14 It asked the correspondent to indicate 13 specifically occasions of dates, times, locations, amounts 16 and parties involved for which such effects are known, and, 17 in making a comment on this question ten to Bill 18 Papageorge, who would be responsible for Monsanto's re 19 sponse to the SPA, I was trying to express a concern that, 20 in trying to succinctly and precisely to respond in an open 21 fashion to question ten, that there were issues of judg 22 ment, and that we needed to be very clear and get consensus 23 that this indeed did represent a corporate position in our 24 responses. 25 1 allude to Yusho because there had been an
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1 awful lot of inaccurate reporting about exactly what was 2 the Yusho incident,, who was involved, what had been the 3 4 Q. Well, let me ask this questions Number ten 5 asks, as you indicated, for a description of any adverse 6 health or environmental effects which you know or believe 7 to have resulted from the introduction of PCBs compounds or 0 mixtures into the environment, and then it asks for 9 specific information, and on Exhibit 358 regarding that 10 question you begin with none, question mark. Why did you 11 put none, question mark? 12 A. Because this was at a time when there were 13 allegations that perhaps PCBs were carcinogenic, and so, in 14 answering any type of response of this sort, by putting 15 those words with those question marks, I was saying there IS needs to be some discussion, some debate as to, is there 17 any limit to the severity of affect. We need to -- Let's 18 talk adout it, Bill. 19 Q. And by putting "hone,8 was that intended as 20 an expression of prior corporate response to similar types 21 of questions? 22 MR, FEATHERSTORE; Object to the form. 23 A. No. I don't believe that was so. 2 4 Q, (by Mr. Bradley) Aren't you basically saying 25 here in Exhibit 358, "Gees, maybe we shouldn't tell them
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1 anything. Maybe we should toll them about Yusho. Maybe we 2 should tell fchera about chloraene that happened years ago." 3 That* a a pretty dangerous question? isn't that basically 4 what you're saying there? 5 A. Mo, I think that's your interpretation of
6 what you think was in ray mind. It's not what I've just
7 stated was in my mind.
8 Q, Tell me -- I didn't understand your answer on
9 why you would list "None" for a description of any adverse
10 nealth or environmentai effects. Did you believe that
11 "None" would be an appropriate response to question ten?
12 A. I think that "None" could have been appropri
13 ate as a response to adverse human health effects.
14 Q Well, the question says, "A description of any
15 adverse nealth or environmental effects..." Now --
16 MR. FEATHERSTONE? Well, chat's not what it
17 says, so let's get it right.
which you know or believe
18 to have resulted from the introduction of PCS compounds or
19 mixtures into the environment,"
20 HR. BRADLEYj That's the reason that I talked
21 about environmental effects, Mr. Feather stone, is because
22 he had talked about adverse human health effects, I was
23 just trying to broaden it.
24 But in 1975 you were aware of the report by
25 Hr. Jensen describing PCBs in the environment; is that
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1 true? 2 A. I saw the report of Mr. Jensen which reported 3 the presence of a previously unidentified chlorinated 4 species in the environment. That's all he was reporting, 5 the presence of a chlorinated species hitherto unidentified 6 in the environment. 7 Q. Lets me ask you this question, then, Mr. Woods 8 By 1970 didn't you believe that PCBs were present in the 9 environment and were having some adverse affect on the 10 environment? 11 A. No. 1 believed the PCBs were in the environ 12 ment. I would have been guilty of the worst sort or specu 13 lation had I tried, frosa my knowledge base at that point in 14 time, to say what was the effect of those compounds in the 15 environment. 1G Q Did you ever believe that PCBs in the environ 17 ment caused eggshells to thin? 18 A, I believe that chlorinated species in the 19 environment could be connected with eggshell thinning. I 20 did not -- I was not capable at any time prior to 1975 of 21 really being able to satisfy myself intellectually that 22 PCBs were directly involved in eggshell thinning. 23 Q. What did you mean when you wrote on Exhibit 24 358, "Chior acne years ago - Dangerous Question,H with a 2 5 hyphen in between there?
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1 A. The hyphen In between was not relating the 2 dangerous question to chloracne. I was merely pointing out 3 that, in terms of the adverse effects, or adverse health 4 effects of PCB, chloracne had been raised as an adverse 5 affect of PCBs. That had nothing to do with their presence 6 in the environment in the sense that this question was 7 oeing askea. I mean, that was their presence in the work8 pi ace which was leading to -- had been related to lead to 9 cal oracne years ago. 10 And the question said, "..that you know or 11 believe to have resulted from the introduction of PCB 12 compounds or mixtures into the environment." Chloracne was 13 associated with its presence in the workplace, so it was 14 purely an industrial hygiene question, and I wanted to know 15 how Bill was going to handle that. 1G I then put a hyphen there, because I'm saying 17 now, the dangerous-question comment in this item twelve, it 18 relates to the whole of question ten in the EPA document. 19 So I said this is a dangerous question because by 1975 we 20 had already experienced as a corporation the ability of 21 people to take an honest display of information by Monsanto 22 and to extend that into speculation, conjecture-, and to 2 3 departures which the information did not support, and 24 therefore, I'm saying that there is an issue here of danger 25 in how we respond to that question.
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1 Q, By 1975 you've already Indicated to us that 2 either Mr. Beni gnus or Mr. Papageorge had made a review of 3 the early studies regarding chloracne and determined that 4 they did not relate to PCBs. Is that correct, or am I 5 misunderstanding what you told us previously? 6 A. Yes, you are. 7 MR. FEATHERSTONE: Or misstating. 3 THE WITNESS: Well, certainly misstating, if 9 not misunderstanding. 10 Q. (by Mr. Bradley) What was the prior review of 11 -- Let me ask it this way: By 1975 had there been a review 12 raaae of the previous medical literature of chloracne 13 regarding similar symptoms in the thirties and forties, but 14 whicii either Mr. Beni gnus or Hr, papageor ge determined did 15 not relate specifically to PCBs? 16 A. WGW . 17 MR. FEATHERSTONE: Object to the form. 1 8 THE WITNESS: That is still a misstatement of 19 wuat we talked about earlier today. 20 MR. FEATHERSTONE: Well, all right. But all 21 he asked is did that happen, and if it's a misstatement, 22 then the answer is no. 23 A. No. 24 Q, (by Mr, Bradley) Okay, Was there a review 2 5 made of previous medical literature of chloracne by Mr.
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X Benignus or Hr. Papageorge prior to 1975? 2 A. No. 3 Q. Did Mr. Benignus or Mr. Papageorge ever make a 4 review of any literature regarding chloracne? 5 MR. FEATHERSTOMEj Objection. Calls for 6 speculation. 7 Q. (by Mr. Bradley) Go ahead and answer. 8 A. I don't know. I do not believe that either 9 Mr. Beni gnus or Mr. Papageorge personally reviewed the 10 previous literature about chloracne, because neither of 11 them was competent so to do. 12 Q Did either Mr. Benignus or Mr. Papageorge 13 inform you that a review had been made of previous medical 14 literature on chloracne? 15 A. Mr. Benignus or Mr. Papageorge, as part of my 16 education when I carae on board, told me what their latest 17 thinking was about chloracne and PCBs. 18 Q, Did they tell you -- 19 A. The basis of that I do not know. 20 Q. Did they tell you that a review had been made 21 of previous medical literature on chloracne? 22 A, I believe somebody told me that the informa 23 tion had been reviewed, 24 q. Did somebody tell you that, as a result of the 25 review, that they determined subsequent generation of
- 113 CONCANMOM JAEGER
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COMPUTER AIDED TRAMSCRIPTIOR
1 medical information indicated that those symptoms that were 2 reported in the thirties and forties did not relate 3 specifically to PCBs? 4 A. Yes. 5 Q. Why then, Mr. Wood, would you in Plaintiff's 6 Exhibit 358, item twelve, regarding question ten of Exhibit 7 357, write, "Cloracne years ago" in relation to a question 8 that asked for a description of any adverse health or 9 environmental effects which you know or believe to have 10 resulted from the introduction of PCB compounds or mixtures 11 into the enviroruaent ? 12 A. Irrespective of whether I believed chi or acne 13 was associated with the use of PCBs previously, there is no 14 question that there was a record which stretched for years 15 of people believing and people misstating causal connec 16 tions between chi oracne and PCBs. And it was clear to me 17 that as we respond to this particular BPA questionnaire and 18 as other people respond to this EPA questionnaire, that 19 there was a potential for old mythology to renow Itself. 20 Q. Part of the reason you described question ten 21 as a dangerous question is because you believed it would 22 require Monsanto to tell that it knew that there were 23 probleras associated with PCBs that it hadn't informed the 2 4 public aboutj isn't that true? 25 A. Mo.
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1 Q. Mr. Wood, I'm going fco show you Plaintiff's 2 Exhibit 1675. Have you -- Let me ask it this way. Are you 3 familiar with a 197 5 or 1977 report from fJXGSH on PCEs? 4 A. I recall that there was a report from MIOSH in 5 that sort of time frame on PCBs. 6 Q, Do you recall whether you reviewed the KIOSK 7 report that was generated sometime around '75 to '77? 8 A. It would have been reviewed by the department 3 within Monsanto that should review such data to give it 10 their -- who were technically equipped to so review, and 11 they would then -- normally they would either discuss with 12 the business group or write to the business group telling 13 us what they believed the -- was an appropriate executive 14 summary of drawing our attention to what they felt were the 13 critical public issues surrounding such a document. IS Q. Perhaps ray question wasn't clear. My question 17 was, do you ever recall reviewing a -- Well, let me ask it 18 this way; I'm now' going to show you Plaintiff's Exhibit 19 1373 and ask you whether you have ever seen that document 20 before, 21 A. No 22 Q. is this the report *-- Well, would you know 23 whether this is the report of NIOSH that you were referring 24 to as being generated in the 1975**to~l977 time frame? And 25 I refer you to the reference just above the date at the
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1 Dottow of the document. 2 A. I knew that NI05H published a report in that 3 time frame. Whether this particular document that I'm 4 looking at, which is a document which has an HEW cover but 5 with a NIOSH subhead down here --- since I know that the 6 NIOSH document published at that time related to exposure 7 to PCBs, I surmise that this is the document to which that 8 was referring. 9 Q. Ail right. Mr. Wood, I'm going to represent 10 to you that Plaintiff's Exhibit 1675 is a copy of the 11 reference section out of 1373. And if you would, for a 12 moment, I'd like you to compare the pages to make sure that 13 ray representation is accurate. 14 HR. FEATHERSTONE: Well, do we need to do 15 that, or can we just simply assume that your representation 16 is accurate? Is that acceptable to you? It's acceptable 17 to us. 18 MR. BRABLEY: Yes. That's fine. 19 Now, my question, Mr. Wood, is, which of the 20 references listed on Plaintiff's Exhibit 1675 give you -- 21 A. That's this reference? 22 Q. (by Mr. Bradley) Yes. 23 A. 1675? 24 Q. I'm going to start the question all over 25 again. Which of the references listed on Plaintiff's
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1 Exhibit 1675 relate.to any adverse health or environmental 2 affects which you know or believe to have resulted from the 3 introduction of PCS compounds or mixtures into the environ 4 ment --* 5 MR. FEATHERSTONEs Object to the question. 6 Q. (by Mr. Bradley) --> that precedes October 17, 7 1975? 8 And I assume you object to that, as well. 9 MR. FEATHERSTONE % I do. I object to the form 10 and object to the harassing nature of tile question and 11 object to the form of the question. 12 THE WITNESS s Anything else? 13 MR. FEATHERSTOMSi Well, I'll think about it 14 while you try to figure out how you'd ever answer a ques 15 tion like that. 16 THE WITNESS: Weil, I can't answer a question 17 like that. 18 Q. (by Mr. Bradley) Do you know whether any of 19 the references listed on Plaintiff's Exhibit 1675 relate to 20 adverse health or environmental effects alleged to have 21 resulted frora the introduction of PCB compounds or mixtures 22 into the environment? 23 A. To answer that question we're going to have to 2 4 go through this one by one, and if I can recall having seen 25 the particular study, then I'll have to make a judgment as
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i to whether I have any comment about any potential hazard. 2 It we're going to do that, we'd better get to it. 3 MR. FEATHERSTOME: Off the record. 4 (Thereupon, a discussion was had.) 5 Q. (by Mr. Bradley) Have you completed your 6 review of the references on Plaintiff's Exhibit 1675? 7 A. Yea, X have. 8 Q. Would you answer my question now? 9 A. None of these references leads me to change my 10 conclusion about the adverse health questions on human 11 beings resulting from the introduction of PCB compounds or 12 mixtures into the environment. 13 As a clarification of an earlier answer, I am 14 that coraraent is restricted to adverse health effects 15 resulting from the introduction of RGBs into the environ 16 ment . 17 0. And how -- Do any of the references on Exhibit 18 1675 -- Just a moment. 19 X'ai going to stop that question and go back 20 and ask you to read the question that he's responding to 21 that I posted to him just before the break. 22 (Thereupon, the reporter read back the question.) 23 Q, (by Mr, Bradley) Mr. Wood, I appreciate the 2 4 answer you have given me, and that partially answers my 25 question. Are there any references on Plaintiff's Exhibit
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X 1675 that relates to any adverse environmental effect which 4o-t may have resulted from the introduction of PCS expounds or 3 mixtures into the environment? 4 hm X have not reviewed this list of reference on 5 1675 from the total viewpoint of effect on the environment. 6 Monsanto conceded very early on in our deliberations on PCB 7 that PCB was present in the environment. I'm trying to 8 wend my way through this one. If it*s not responsive then 9 stop me. 10 HR. FEATHERSTONEj Bet's go off the record for 11 a second, and maybe we can come -- 12 MR. BRADLEYs Okay. 13 {Thereupon, a short colloquy was had.) 14 0. (by Mr. Bradley) Back on the record. Let me 15 ask it this way, Mr. Wood; In October, 1S75 were there 16 adverse environmental effects which you knew or believed to 17 have resulted from the introduction of PCB compounds or IS mixtures into the environment? 19 A. There was the adverse affect of there being 20 present in the environment unbiodegraded synthetic material 21 which was capable of bioraagnification in food chains. 1 22 consider that an adverse affect. 23 Q. Any other adverse effects, adverse environ 2 4 mental effects? 25 MR. FEATHERSTONE: That the witness knew
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1 about ?
2 Q, (by Mr. Bradley) That you knew or believed to
3 have resulted from the introduction of PCB compounds or
4 mixtures into the environment in 1975. 5 A. At that stage my knowledge of the adverse
6 environmental effects was presence and the biorefractory
7 nature of the material that was present.
8 Q. Do you now have in front of you Plaintiff's
9 Exhibit 1475?
10 A, Yes. Is that an exhibit that you have seen
11 before? ir>. A.
Yes, it is,
13 Q. Is this a letter from Douglas Hardy to you,
14 among others, dated January 12, 1967?
15 A. Yes.
16 Q. Is the subject matter "hr odor - Sweeten"?
17 A. tea,
10 Q. Is this a true and accurate copy of the letter
19 written to you and others by Douglas Hardy on that date?
20 A. Yes.
21 Q, Is this a document that you maintained in your
22 files at Monsanto as part of Monsanto"s regularly-conducted
23 business?
2 4 A. Yes. 25 Q. is that the Monsanto letterhead in the top
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1 left-hand portion of that exhibit? A. Yes.
3 Q Would you now put infront of you Plaintiff's 4 Exhibit 1498? 5 A. Yes. 6 Q. Is your namelisted on the topright-hand 7 corner as someone who received a carbon copy of this? 8 A. It is. 9 Q* Is this a document you have seen before today? 10 A. Yes 11 y * And is this a memo w r i tfcea by R. A. Baxt or to 12 . Keller da tea A ugust 19th, 197 5? 13 A. Yes F it is. 14 Q* And is this a true a net accurate copy of the 15 or timit you r ece ived a copy of f rom R * ti Baxter to R. IS .ell or da ted Augu st 19th, 19 7 5? 17 A. It is. except I wa e not previous ly privy to 18 comment on t his particular copy H. S Be r gen made * 19 Q. Pardon me? 20 A. I had not previously seen the additional hand 21 written comment that was made by somebody who received this 22 copy other than myself. 23 Q. You mention the name H. S. Bergen, Does it 2 4 appear to be* his handwriting? 25 A, I can* t tell whether that is Howard's copy or
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1 whether this is somebody elee's? X can't make out the 2 signature or the initialing' of the comment. 3 Q. Can you make out what the comment is? 4 A. NO. 5 Q. Does it appear to you to say European 6 something? 7 A. Again, speculating, I read it as "European 8 trip," but -- c Q. Okay. And is this a memo that you maintained 10 m your files at Monsanto as part of Monsanto's regularly11 conducted business? 12 A. Yes. 13 Q, And this also has the Monsanto letterhead in 14 the top lef t-hand corner ? 15 A. Yes, it does. 16 Q. Would you now examine Exhibit 1425? 17 A Yes. 13 Q. Is this a copy of a memo you wrote to W. B. IS Papageorge on August 29, 1975, regarding an August 29, '75 20 telephone call? 21 A. Yes, it is. 22 Q. Did you write this memorandum shortly after 23 you received the telephone call? 24 A. Yes, I did. 25 Q. Is this a true and accurate copy of the memo
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1 you sent to W. B. Papageorge dated August 29, 197 5? 2 A. Yes, it is. 3 Q. Did you maintain a copy of this exhibit in 4 your files at Monsanto as part of its regularly-conducted 5 business? 6 A. Yes, I did. 7 Q. Would you now look at Exhibit 1117? 8 A. I have it. 9 Q. On the top right-hand portion of that it indi 10 cates you received a carbon copy or thisy is that correct? 11 A. Tnat is correct, )L o Q. And this is a letter from R. E. Keller to R. 13 Baxter dated August 15th, 1375 on the subject of chlori 14 nated dibens ofurano? 15 A. Yes. 16 Q. What does the LLJJ hyphen 50 45 indicate under 17 Pc, Baxter's name? 18 A. At that stage, our European Technical 19 Laboratory had moved from Ruabon in Worth Wales, Englana, 20 to Louvain-La-Deuve, Belgium, and the mail sone relative to 21 that location was 5045. 22 Q, There*a also some handwriting on it which 23 appears to say "European trip file folder, pis," which I 2 4 assume means "please." 25 A. That* s ray assumption. It's not my handwrit-
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1 ing. 2 Q. All right. And other than the handwriting, is 3 this a true and accurate copy or the letter that you 4 received a copy of, dated August 15, * 75, from R. E* Keller 5 to R. Baxter? 6 A Ye s * 7 Q, And is this a document that you maintained in 8 your files at Monsanto as part of Monsanto"s regularly9 conducted business? 10 A. Yes. 11 Q. Does this also have Monsanto's letterhead on 12 the top left-hand portion of the exhibit? 13 A. Yes, it does. 14 Q. I now ask you to look at Plaintiff's Exhibit 13 12 42 . 16 A, Okay. 17 Q. This document indicates that you were a 1 8 recipient of this exhibit with an attachment from G. to you 19 and a variety of others? is that correct? 20 A. Yes. 21 Q. And it's dated February 10, 1975? 22 A. Yes, it is. 23 Q. Subject matter is "Westinghouse"? 2 4 A. Yes, it is. 2 5 q. It says, "Attached is a xerox copy of the
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1 Westinghouse Codicil Mo. 1 which is part of the contractw? 2 A. Yes, it dose. 3 Q. Who is C.? 4 A. I think this is related to Gladys Burgos in 5 the Hew York offices who is the "frora" in this particular 6 nemo. 7 Q. And is this a true and accurate copy of the 8 ietter she sent to you and others dated February 10, 1975? 9 A. I believe so. 10 Q. Okay. Is this a document you maintained in 11 your the tiles at Monsanto as part of its regularly12 conducted business?
!
13 A. C. Paton is asterisked, receiving theoriginal 14 copy? Ray Ford received an original carbon copy? and the 19 way that the contract files were maintained, certainly 16 those tiles would have been maintained. I'm not sure that 17 I would have kept my copy of this particular document on 18 tile because it would have been part of the corporate 19 contract file. 20 q. But Monsanto would have retained a copy? 21 A. Yes. 22 Q. Okay. AndI111 ask you to look at Plaintiff's 23 Exhibit 1419, Have you reviewed it? 24 A. Yes. 25 Q. Is this acopy of a letter from you to Hike
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1 Hodan dated November 7, 197 5? 2 MR. FEATHERSTOME; Minor point: This letter 3 has a bunch of attachraents to it which aren* t here. Are 4 you just asking him to verify that this is a copy of the 5 cover letter? 6 HR. BRADLEY: Yeah. I*11 just get to that. 7 That is not a minor point? it*s a major point. 8 This doesn* t have the attachments referred to 9 in the letter? is that correct? 10 A. This is correct, 11 MR. FEATHERGTOME: All right. When I said ray 12 minor and mag or, it was not about the significance of the 13 attachments, just in responding to the question, 1 want it 14 made clear that this is a true and correct copy of the 15 cover letter that went with all these attachments. We will 16 sticmi&te that there were attachments with it. 17 HR. BRADLEY * We*11 stipulate that the attach 16 ments are not part of the exhibit. Is that correct? 19 MR. FEATHERSTOME: Yes. I also stipulate that 20 the attachments went to Hodan, too. 21 MR. BRADLEY: Off the record. 22 (Thereupon, a short colloquy was had.) 23 Q (by Hr. Bradley) And is this letter a cover 24 letter that had attached to it the references that are 25 referred to in the exhibit?
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1 A, Yes, it is. 2 Q. And the exhibititself doesn't have the 3 attachments, correct? 4 A. It does not. 5 Q. And is this a true andaccurate copy of the
6 letter written by you November 1, 1975 to Michael Modan
7 absent the exhibits?
8 A. I presume it is, but just as a matter of
9 reference, this is the first copy I've seen so far where we
10 have such a striking difference between pages of the copy.
11 There is a very distinct difference in page one and page
12 two, but this would seem to be a representative copy of the
13 memo at November 7th, 1975.
14 Q. is this adocument that you maintained in your
15 riles at Monsanto as part of Monsanto regularly-conducted
3.6 business?
17 h, h cover letter, yes.
18 Q. Okay. Would you now look at Exhibit 1510?
19 A. Yes.
20 Q. At page 317 of Plaintiff's Exhibit 1510 is
21 there a paper authored by you entitled "Chlorinated
22 Diphenyl Dielectrics - Their Utility and Potential Substi
23 tutes"?
2 4 A. There is.
0R
Q. And does thatcontinue onthrough
page324 of
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COMPUTER AIDED TRAM SCRIPT I Oil
1 that exhibit? 2 A. Yes, it does. 3 Q. Is that a true and accurate copy of a report 4 that you prepared? 5 A. Yes, it is. 6 Q. Did you maintain a copy of this report in your 7 files at Monsanto as part of Monsanto's reguiarly-conductea 8 business ? 3 A. Yes, 1 did, 10 Q. The beginning of Plaintiff's Exhibit 1510 11 refers to "Session V, Economics and Substitutes." Turn to 12 the first page of the exhibit, 13 A, Uh-huh. 14 Q Did you present this paper at a conference? 15 A. I presented this paper at a conference at the IS Pitt Hotel in Chicago in November of 1975. 17 Q. And that was as part of the National 18 Conferonce on Polychlorinated Biphenyls, November 13 to 21? 19 A. Yes, it was. 20 Q, And I'd asked you to refer to Plaintiff's 21 Exhibit 1509. Does Plaintiff's Exhibit 1509 also contain 22 the report that is referenced in 1510 beginning at page 317 23 and ending at 324? 24 A. Yes, it does. 2 5 MR. FEATHERSTONES Are you going to attach
- 128 CONCANNON & JAEGER
WATER PCB-SD0000056568
COMPUTER AIDED TRANSCRIPTION
1 1509 to the transcript? 2 MR. BRADLEYs I was not intending to. 3 MR. PEATHERSTOHE: Would you just describe on 4 the record what 1509 is? 5 MR. BRADLEYs I'd be happy to do that. 1509, 6 the top right-hand, it says O.S. Department of Commerce, 7 Rational Technical Information Service, PB-253 248, and 8 it's entitled "Rational Conference on Polychlorinated 9 Biphenyls," November 19 to 21, 1975, Chicago, Illinois. 10 It begins with Bates number 774190 and ends at 11 Bates number 774S67. 12 HR. FEATHERSTOMEi That's the Nevada Power 13 Bates number? 14 MR. BRADLEYi Yea. 15 Why did you write Plaintiff a Exhibit 358 -- 16 Let me rephrase the question. I take it the letter 17 referenced at Plaintiffs Exhibit 357 came to you in 1C October of 1975. 19 A. Ho. 20 Q, (by Mr. Bradley) To whom did it go? If you 21 know. 22 A. I believe that this would have gone to Mr. 23 Papiga or go 2 4 Q. And did Mr. Papageorge send it to you? 25 A. I believe he would have done that.
- 129 CONCANNON & JAEGER
WATER PCB-SD0000056569
COMPUTER AIDED TRANSCRIPTION
1 Q. Why would he have done that? 9 A. Because Mr. Papageorge and I and our technolo 3 gy comaunity would discuss how Monsanto should openly and 4 responsively respond to such a letter. 5 Q. In October of *75, were you manager of 6 dielectric fluids? 7 A. Yes, I was. 8 Q. In October of *75, what title did Bill cj Papageorge have? 10 A. I'm not sure whut his title was at that point 11 in time. His function was that of product stewardship. 12 Q. Is -- Do you know why Mr. Papageorge was the 13 person who was chosen to respond to the October 17, 1975 14 letter from the United States Environmental Protection IS Agency, versus you, for example, who was manager of 16 dielectric fluids? 17 A. Because most of Monsanto* s relationships with 1 s the Environmental Protective Agency were conducted by 19 people who had, as part of their role, the routine - 20 Sorry. None of this was routine -- people who had the 21 responsibility to coordinate Monsanto*s product safety 22 moves with the EPA. 23 Q. And that was Mr. Papageorge? 2 4 A. That was Hr. Papageorge. 25 MR. BRADLEYi 1 have nothing further.
- 130 CONCANHON & JAEGER
~_
" WATER PCB^SDb000056570
(JU li.fc'U 'XlUiX tXJLUEi U iiuuHJW.i,- *
1 UR, FEATHERSTONE 8 Great. No questions.
2 3
4 5
of v
D f 1993 *
7 MY COMMISSION EXPIRES
o
8
9
10 NouarV Public, within and for^feiie State of Missouri
11
12 OMifi.iifra!is
WARY muc STATE Of fflSSQH! 13 ST.OWaLgSCOgSTY
w cornissias exp. MAq.1q.1095 14
15
16 17
18
19
20
21
22
23 24 25
- 131 -
CONCANNON & JAEGER
WATER PCB-SD0000056571
COMPUTER AIDED TRANSCRIPTION
1 STATS OP MISSOURI ) ) S3
2 COUNTY 0? ST. LOUIS ) 3 If Mark D. Concannon, a Notary Public within and for 4 the State of Missouri, duly commissioned,, qualified and 5 authorised to administer oaths and to take and certify to 6 depositions, do hereby certify that pursuant to Notice in 7 the civil cause now pending and undetermined in the 8 District Court of the United States, within and for the a District of Nevada, entitled NEVADA POWER COMPANY, Plain 10 tiff, -vs- MONSANTO COMPANY, et al., Defendants, to be used 11 in the trial of said cause in said Court, I was attended at 12 the law offices of Messrs. Husch & Eppenberger, 100 N. 13 Broadway, in the City of St. Louis, State of Missouri, by 14 Ralph A. Bradley and Richard Hinckley, attorneys for the 15 Plaintiff? by Bruce A. Feather stone, attorney for the16 Defendant, Monsanto? by Laurie Basch, attorney for the 17 Defendant, Westinghouse? and by DAVID WOOD, the witness, in 18 said office on April 1, 1993. 19 The said witness, DAVID WOOD, being of sound mind 20 and being by me first carefully examined and duly cautioned 21 and sworn to testify the truth, the whole truth and nothing 22 but the truth in the case aforesaid, thereupon testified as 23 is shown in the foregoing transcript, said testimony being 2 4 by me reported in shorthand and caused to be transcribed 25 into typewriting, and that the foregoing pages correctly
- 132 -- COM CAME Oil & JAEGER
WATER PCB-SD0000056572
COMPUTER AIDED TRANSCRIPTION
1 set out the testimony of the aforementioned witness,. DAVID
2 WOOD, together with the questions propounded by counsel and
3 the remarks and objections of counsel thereto, and is in
4 ail respects a full, true and complete transcript of the
5 questions propounded to and the answers given by said
6 witness? and that said testimony, so transcribed, was
7 subscribed to by the witness on the _______ day of
8 , A. D., 1993.
9 1 FURTHER CERTIFY that I an not of counsel nor
10 attorney for any of the parties to said suit, nor related,
11 nor interested in any of the parties or their attorneys.
12 WITNESS HY HARD and Notarial Seal, given this
13
day of _________ ___________
. A. D. , 1993 , at St. Louis,
14 Missouri.
15 MY COMMISSION EXPIRES MARCH 21, 1994.
16
17
18 MARK D. CONCANNON,
19 Notary Public, within and for the State of Missouri
20
21
22
23
24
25
- 133 -
CONCANNON & JAEGER
WATER PCB-SD0000056573
COMPOTER hiDBD TRAM8CR1PTION
1
2
3 Concannon and Jaeger General Court Reporters
4 705 Olive Street, Ste. 504 St. Louis, Missouri 63101
5 May 3, IS93
6
7
6 David Wood Safiex Business Director-Araericae
9 Monsanto Cheiaical Company 000 North Lindbergh Boulevard
10 St. Louis, Missouri 63167
11 Re; Nevada Power Vs. Monsanto
12 Dear Mr. Wood;
13 This letter, incorporated as the last page of your deposition, taken on April 1, 1993, will serve as notice to
14 you that your testimony is now ready for your reading and signing of same.
15 I would appreciate your contacting my office by
16 calling (314) 421-1000 within the next thirty days so that arrangements can be made to accomplish this before your
17 deposition must be filed in Court.
1 0 Thank you for your cooperation in this regard.
19 Sincerely,
20
21 MARK D. COMCANNON
22
23 M DC jrak
24
25
- 134
CONCANNON & JAEGER
WATER PCB-SD0000056574
COMPUTER AIDED TRANSCRIPTION
1 DAVID WOOD
2
3 - DEPOSITION CORRECTION SHEET -
4 In Res NEVADA POWER Vb. MONSANTO
5 Upon reading his deposition transcript and before subscribe ing thereto, the deponent indicated the following:
6
7 Page
Line
should reads
8 Reason assigned for changes
9 Page
Line
should read:
10 Reason assigned for changes
11 Page
Line
should reads
12 Reason assigned for changes
13 Page
Line
should reads
14 Reason assigned for changes
15 Page
Line
should reads
16 Reason assigned for changes
17 Page
Line
should reads
18 Reason assigned for changes
19 Page
Line
should reads
20 Reason assigned for changes
21 Page
Line
should reads
22 Reason assigned for changes
23 Page
Line
should reads
24 25 DAVID WOOD
- 135 -
CONCANNON & JAEGER
WATER PCB-SD0000056575
COMPUTER AIDED TRANSCRIPTION
1 DAVID WOOD
2
3 - DEPOSITION CORRECTION SHEET -
4 In Re NEVADA POWER Vs. MONSANTO
5 Upon reading his deposition transcript and before subscrib ing thereto, the deponent indicated the following:
6
7 Page
Line |"7 should read xlOJj-'Lb ncyb
8 Reason assigned for change 9 Page ptZ. L ine ^ should read: (dab
10 Reason assigned for change Page 37 Line j/flshould read;
11
12 Reason assigned for change
13 Page
a>iNf ^ Line b" should read
14 Reason assigned for change 15 Pageb'j' Line 43 should read; ,el/c,
16 Reason assigned for change
17 Page ^ L ine
should read;
18 Reason assigned for change ?c6-J nA
19 Page <17 Line 3 should read;
S
20 Reason assigned for change
21 Page
Line should read
22
23 Page
Line
24
25
WATER PCB-SD0000056576
,CF`.!T BY:
3-31-83 ; 2:34PM ; BRADLEY AND MERRELL-*
314 331 9029;# 2/ 8
'A% SS&7 |
UNITED STATE ENVIRONMENTAL PROTECTION AGENCY
WASHINGTON. D.C. 20460~
OCT 17 1975
emet or enforcement
Monsanto Industrial Chemicals Company 600 N. Lindbergh Boulevard St. Louis, Missouri 63166
^2 WIS
Gentlemen:
T, .
.
Recent governmental sampling data indicate the presence of
Polychlorinated Biphenyls (FCBs) end comparable chemical substances
Is the alrf In vater bodies, and In fish In several areas of the
country. In order to determine the nature and extent of the possible
adverse effects resulting from the presence of PCB compounds In the
environment, the Environmental Protection Agency (EPA), in cooperation
with other federal and State egenciea, is attempting to determine the
sources end amounts of PCBa entering the environment. It le important
that this effort be carried out without delay.
:
It is our understanding that your company handles PCB compounds
or mixtures or comparable chemical substances in its operations. I am therefore requesting, pursuant to the authority provided by Section 308 of the Federal Water Pollution Control Act, as amended, 33 U.S.C. 1318, end Section 114 of the Clean Air Act, as amended, 42 U.S.C. 1857c-9, that your company furnish EPA with information pertaining to your use end handling of PCBs and comparable chemical aubstances. In addition to a general description, which should include information as to sources, quantities, usee, end ultimate disposition, you should respond in detail to the enclosed questions. If any question
Is not applicable to your company or operations, please so indicate by responding ''not applicable."
J The information requested herein must be provided notwithstanding its possible characterization as confidential Information or trade ' secrete. tShould you to request, however, any Information (other than effluent or emission data) which the Administrator of this Agency determines .to constitute methods or processes entitled to protection as trade secrets will he maintained ap'confidential, pursuant to procedures specified in 40 CfH Path 2k
I
Koni?81 ADM 006290
WATER PCB-SD0000056577
3-31-83 : 2:34PM ; BRADLEY AND MERRELL-
314 331 9029;# 3/ 8
2
-- Wittain 14 davi of receipt of this letter, your company buss
"^provide HI infopnation concerning your current status and activities
and cov$dng the'twelve month period Immediately preceding receipt of
-tetter.
^
.
Within 30 days famoving receipt of this letter, your company
oust provide all information for all of the prior years indicated.
4
1
i
The information required herein should be sent directly to
the address indicated below. If you have any questions you may
cell*tlie pe'rsbh 'ihdlcatad below or Mr. Blake A. Biles of our office
:U.i202>.,.755-8731.
We appreciate your prompt cooperation in this matter.
Enclosure
Regional Contact: ' > Mr. Earl X Stephena&fi Director, Enforcement Division Environmental Protection Agency 1735 Baltimore Kansas City, Missouri 64108 Telephone: (816) 374-2576
;* /
6
Knm?.82
ADM 006291
WATER PCB-SD0000056578
SENT BY:
- -f '
-31-83 2:35PM ; BRADLEY AND MERRELL-
314 331 9029;# 4/ 8
"I"
POLYCHLORINATED BIPHENYL (FCB) COMPOUNDS OR MIXTURES
" . ' Within 14 days of receipt of this letter, your company must
provide <11 information concerning your current status and activities
-mi covering the^tvelve* month period immediately preceding receipt of
this letter.
<v
'.
* ' Within 30 days fHaving receipt of this letter, your company 4. Bust provide ell information for all of the prior years indicated.
0?
FOR PURPOSES OF THIS LETTER, THE PHRASE "PCB COMPOUND OR
MIXTURE" INCLUDES ALL CHEMICAL SUBSTANCES KNOWN OR BELIEVED BY
YOU TO BE PCB COMPOUNDS OR MIXTURES OR OF A SIMILAR CHEMICAL
NATURE, IRRESPECTIVE OF TRADE NAME, AND SPECIFICALLY INCLUDINGy
CHLORINATED TERPHENYLS..
.
eA
1. For each FCB compound or mixture produced or isguax&BjLb? your
company, for each company facility, during tech year of 1971.
1972^1973._19J4and the first tvo quarters of 1973_l_
"
'a. The total amount of each FCB compound or mixture produced
-
or imported. '
,
.
b. The name end address of each of your company's facilities ^ ll
which handle PCB compounds or mixtures, (including production
facilities and wholesale end retell outlets), end the
. .Jgj)
amount of each PCB compound or mixture distributed through ^ .
. each facility.
c. The name and addreas of each customer of each PCB compound
or mixture, the amount of each PCB compound or mixture
. obtained by each customer from each facility, and each
customer's delivery point(a) for the receipt of each PCB
compound or mixture. .
;'
*.
2. For each FCB compound or mixture incorporated by your company
into its products, for each company facility, during each -
year of 1971, 1972, 1973, 1974, and the first two quartern
of 19751 '
.
* a. A description of each product / '
b. . For each product the total amount incorporated of each ' FCB compound or mixture.
10(119Ki AO* 006292
WATER PCB-SD0000056579
3-31-83 ; 2:35PM ; BRADLEY AND MERRELL;
314 331 9029:# 5/ 8
~7Z (continued) " "
* ' *
t
t -
ev-For eaeh produce the name and address of each source from
vhiclTyour company obtained each PCB compound or mixture,
and the amount 4f each PCB compound or mixture obtained from
each aource.
d. The name and address of each of your company's facilities which handle such products (including production facilities
and wholesale and retail outlets), end the amount of each produce distributed through each facility.
e. The name and address of each customer of each product, and i|
. the amount of each produce obtained by each customer from U
each facility. For consumer products list only the total V
production of each product at each facility and the total I
number of customers. Do not provide the name and address 1
of each customer of consumer products.
.
3 For each PCB compound or mixture used by your company in its operations other than for incorporation into its products, for each company facility, during each year of 1971, 1972, 1973, 1974, and the first two quarters of 1975: `
a. A description of each use.
b. For aech use the total amount of each PCB compound or mixture.
c. For each use the name and address of each source from which
, your company obtained each PCB compound or mixture, and the _ ,,
amount of each PCB compound or mixture obtained from each
source.
4. For each PCB compound or mixture reclaimed by your company,
for each company facility, during each year of 1971, 1972, 1973,
' 1974, and the first two quarters of 1975:
''
..
* tB '
'
. v i. A description of each methodof reclamation.
i
'
bi For each method of reclamation, the total amount of " each PCB compound or mixture reclaimed.
e. The total amount of each PCB compound or mixture reclaimed.
KOftl ` ADH 006293
WATER PCB-SD0000056580
3-31-83 ; 2:36PM : BRADLEY AND MERRELL-
314 331 9029',# 6/ 8
d. Th*; name and. address of each source from which your
company obtained fCl compounds^ or mixtures, and the
amount of each PCB compound or*mixture obtained-from
"Sa'ch s ource. '
^
``
e. For each method. reclamation, the location of every
reclamation site,'the name and address of each party
involved In the reclamation of each PCB compound or
mixture, and the amount of each PCB compound or
mixture reclaimed by each party.
For each PCB compound or mixture dlsnosej of by your company
(with or without the Involvement of other parties), for each
company facility, during each year of 1971, 1972, 1973, 1974,
and the first two quarters of 1975:
e. A description of each method of disposal.
.
b. For each method of disposal the total amount of each PCB compound or mixture disposed.
c. The total amount of each PCB compound or mixture disposed.
The name and address of each source from which your company obtained PCB compounds or mixtures, and the
amount of each PCB compound or mixture* obtained from each source.
Wfp**
e.' For each method of disposal, the location of every disposal ' site, the name and address of each party Involved In the disposal of each PCB compound or mixture, and the amount of each PCB
. compound or mixture disposed of by each party.
The composition by chemical name and percent by weight of each
PCB compound or mixture nrodueed. Imported, sold, reclaimed, used,
and/or.disposed of by your company since January 1, 1921.
1
The resulte of eny end all sampling end analysis performed by
your company, its agents or contractors since January 1, 1971,
concerning the following:
'
e. Concentrations of PCB compounds or mixtures in the effluent of eny discharges by the company (into waters of the United States or Publicly Owned Treatment Vorks) or In the emissions of the company into the air. .
|{0rt1?R5 ADM 006294
WATER PCB-SD0000056581
3-31-83 ; 2:36PM ; BRADLEY AND MERRELL-
314 331 9029;# 7/ 8
._b. Tti; flow and/or composition of any discharges or emissions
" bjTth'e company (Into waters of the United States or Publicly
' Oyned Treatment Works, or into the air) which contain PCB
m----- --compounds or mixtures.
'
'
c. Concentrations o^PCB compounds or mixtures in receiving
waters (both upstream and downstream) of any discharges
by the company which contain PCB compounds or mixtures and
concentrations of PCB compounds or mixtures In the air in
. the area of the company,
'
8* The methods by which PCB compounds or mixtures are transported
to, by, end/or from your company, including;
.
a. A description of etch method of transportation, and
the form in which PCB compounds or mixtures are trans** ported by each method. Where different methods of trass**
: portatlon are used at different facilities specify which ' transportation method la used' at each facility.
b. The names and addresses of all known transporters of PCB
. compounds or mixtures.
'
9. All occasions (Including spills) of which you are aware on which t
PCB compounds or mixtures have or may have bsen introduced into
. the environment. In particular, describe such occasions insofar
as they Involved PCB compounds or mixtures in their liquid state,
as Incorporated into closed systems, or as incorporated into
open systems. For each occasion, indicate name and address of
. party involved; dates, time, and location of the discharge or
spillI end the amounts Involved.
''|
10. A description of any adverse health or environmental effects
which you know or believe to have resulted from the introduction
of Pci compounds or mixtures into the environment. Indicate
any specific eeeaeions including dates, times, locations, amounts,
and parties Involved for which such effects ats known.
'
.
; r -
.
11, Aajr end. ell, other Information which you possess concerning:
a. The production, importation, reclamation, use, distribution,
" . end disposal of PCB compounds or mixtures.
_
10019.R6 ADM 006295
WATER PCB-SD0000056582
3-31-83 ; 2:37PM ; BRADLEY AND MERRELL-
314 331 90295# 8/ 8
5
_b. ffcji discharge of PCB compounds or mixtures into the
' . environment. .
.'
In addition to the above| EPA would appreciate receiving any other
information which you possess concerning the distribution and discharge
of PCB compounds or-.mixtures by sources other than your company,
including your company's Customers and sources.
'
,
Vom ?K7 ADH 006296
WATER PCB-SD0000056583
Monsanto TO
David Wood-St. Louis-B2SD Oatober^O, 1975
f-EPA
COMMBITS OH EPA LETT REC'D 10-17
W. B. Papageorge v
B2SK
-\
1. Bill,* this seems to'm be a new version. 2. Page 1. Cl. Terphenyls specifically mentioned.
3. a) Production records answer 1(a).
b) Remember we warehoused PCBs for short period 1974 ahead of
labor contract renewal.
c) Question lc raises a problem that has been at back of -
my mind. #2 report is supposed to show "ship to"
address, but if this is case, why do 3rd party W/GE -
shipments appear under "bill to" locations.
-
4. Q2 a) No problem
b) No problem
c) No problem
'
d) No problem
e) Policy - Hanley level?
,
5. Q3-No problem except 71/72
6. Q4-No reclamation.
7. Q5-a) No problem
A *
b) Difficult. Can split Dielec/HT/Pydraul
1 But some returns mixtures of .oil/PCB, etc.
c) Can do.
.
.`d) Difficult e) Difficult .
} {*
'
8. Q6 -- Available
1
9. Q7 - a) Guess we have b) Guess we have c) Guess we have
10. Q8 - a) Bulk Rail Bulk R - 3 accounts Drum -- Specify drum construction
b) E. M. Potter
AOH 006288
I'nni 988
PLAINTIFF'S EXHIBIT
IN . to R8V. tm
WATER PCB-SD0000056584
11.
Q9 - Should
-------- - -
answer*
from
our
activity?
__
.
-
12. Q10 - None? "Yusho? ^Cloracne-years ago - Dangerous Question.
'\
13. Qll - a) Might get HUB again?
b) Should write this one very carefully - can make some positive points in this section.
/deb
David Wood
vV i i** %
ti t' r
ADM -006289
l ,nni 9R9
WATER PCB-SD0000056585
ROUGH DRA7T - 11/10/5<J,
OUTLINE
.
FGE ENVIRONMENTAL POLLUTION ABATBCOT PUN
5j?r r. ^Introduction S ..
V-
TIL "Problem
ttt. Extensiveness
17. Nature of the Problem RWeerch"andr-medica]ridnpttt
V, Effect on Monsanto
VI. Effect on Customer
VH. Involvement with other producers
Tin. Sources of Contamination
Jkrz--Endiree t-PeHution-
IX. Recent technical changes which have bearing on the contamination
2. Courses of Action
XI. Recommended Course of Action
XU. Implementation of the Recommended Course of Action
A. Immediate Action (12-1-69)
.
B. Interim 1-3 months
C. Short term *= .3-5 months
.
PLAINTIFF'S EXHIBIT
HIT.
ST* 0Z193S
D. Long ter (1-3 jeers) 1. Research medical
5.. Patent.
%4)44
' ^ 2. Manufacturing
6. Environmental Control `
3'. Engineering ' 4. Market
T. Legal
8. public Relations 9- chc: 21
WATER PCB-SD0000056586
nn Probability of Qoeess
rr=P-':
STR 021939
WATER PCB-SD0000056587
c e.
I PGB ETOBC&iMHiTAL PQLLDTICN' ABATEMEOT PLAN Introduction On 15 October the "AD HOC" Committee consisting of Messrs. M. Farrar, P. Hodges, E. John, . Richard, and E. Wheeler issued a report summarizing the polychlorinated biphenyl (PCS) pollution problems from the known available information to date. Out of this report came considerable information, conclusions, and recommendations which we have attempted to tie together into a plan of action in this document. Our objective has been to take a reasonable and responsible approach to the entire problem. Before we get into the problem, we should clarify the meaning of PCB, the nature of the entire line, and how these tie into our product line of Aroclora.
: STR 02 mo
WATER PCB-SD0000056588
Monsanto entered the Aroclor market in 1930 by acquiring Swain Electrical Company or taewn today as. our Anniston, Alabama plant. The first load of Aroclor-which incidentally-- w Aroclor 1254 -- went out of Anniston# Alabama to GE in 1931s J.' Since that time the market has grown to 170 to '200ff4world1d.de.
Chemical Biphenyl
Monsanto Product line
Mature of Material at Ambient
Solid
-5olid-a4 Suhllmes--
Monochlorobiphenyl
l 1
DIChTorab'i
|
c"00'c/
"^ricKlorooi phenyl- -
"Pck;
Quaterchlorobiphenyl
aOO"
Pentachlorobiphenyl
2CSD3-
Eexachloroblphenyl
Aroclor 1221 Aroclor 1232 Aroclor 1242 Aroclor 3248 Aroclor 3254 Aroclor 1250
thin liquid (oil)
thin flush water
oily type fluid '
material
'
Thicker - transmission oil
Heavy-Mo lasses
dick tar
Eeptachlorob^phesyl
Oc^^elro*^rybinhfepyl
Dec&cinoroWphmiyl. <* "
Aroclor 3262 %
Aroclor 1258
Aroclor 32715
Very thick - liquia
Solid . Solid .
STR 021941
WATER PCB-SD0000056589
-3-
c
Total possibility are 210 theoretically possible chlorinated biphenyl i'
&
-
Santow&x or terphesyl Solid
Cl df
rooo;1' Cl c( II. Problem
Aroelor 5460 Solid
Damage to the ecological system by contamination from polychlorinated
$/>
biphenyl (PCB).
'
m. Extensiveness
The problem involves the entire united States, Canada, and sections of
4(J> U
Europe especially the united Kingdom and Sweden. As the investigation broadens other areas of Europe, Asia and Latin America will surely
become involved. Evidence of contamination have been shown 10 some
of the very remote parts of the world. The involvement could and most
likely will follow the DDE investigations.
-
XT. 2^
Nature of the Problem
Professors Widmark and Jensen of the Institute of Analytical Chemistry
at Stockholm, Sweden, in November i960, announced and confirmed finding
PCB in fish, birds, and eggs. Subsequent findings were made in 19S7 ir
Great Britain. In February 19^9* Professor Bisebrough of the Univers It
of California published an article in the Saa Francisco Chronicle
relaying his findings of PCS in the environment of the United States.
Monsanto confirmed the presence of PGB's in sid-1969 and confirmed the
adequacy of work by Widmark and Jensen and others j truly, the PCB's
are a worldwide ecolological problem.
*
STR 021942
WATER PCB-SD0000056590
c -*- c
Analysis indicates the environmental presence of the 5 and higher chlorinated biphenyls which take the appearance of Aroclor 1254 and Arcelor 1260. ' We have strong indications that Aroclor 1242 or at least . .. part of it degrades biologically. Since the Aroclor 1242 contains arou: T percent of the 5 chlorine biphenyl or higher we cannot rule out the possibility that the observations may be a concentration affect of the higher chlorinated biphenyls of Aroclor 1242.
To date there have been no reports of finding Aroclor 1242 present in the environment (except outside the effluent of our plants where we knc Aroclor 1242 is present).
The seriousness of the problem can best be spelled out as follows:
1. Pish - Marine or aquatic species concentrate PCS in the fatty
tissue. Toxic is small quantities (down to 5 ppk) to sensitive max
life such as shrimp.
Birds. - Predatory species feeding on the marine or aquatic life car
further concentrate PCS to possible harmful effects. Specifically
in birds PCS can affect the calcium metabolism leading to egg shei:
imperfections which prevents proper hatch of the young. In fact,
Monsanto has confirmed the eggshell by feeding chickens, a high
order of the species, PCB's in controlled tests.
3. Man - `There is no harmful effect known to man or other mammals aft. 40 years of production. Investigations are underway by various
sources.
STR 021943
4. Political and Public Emotion - PCB's are falsely linked with" DOT
because PCB's show up in the analysis for DDT. PCB's are linked w
other permanent type chlorinated hydrocarbon pesticides. This
becomes particularly serious since about every article, of food in
country is being examined for a trace of these materials.
ST)
ft
--v-t C*"J* C .. rU
f\ r-->
WATER PCB-SD0000056591
(
imra
"Sr j
Cl Cl
-^TYT^ci Of H-C-H Q-C-QI
Cl
1NDR1N
a a
a ci a
UNDANE
J$0
.a ci
WEPTACHLQR
EPOXIDE
CI
C1-OC1
DOT 000
Rg 1 Structural Formulae ef Nine Chlorinated-Hydrocarbon Pv
STR 021944 WATER PCB-SD0000056592
. PESTJCJPBp
ii*' * *r **' 9 Bndrty .'j,.
. > Heptachlor'
/ Dindane ;
y.ti Methoxychlor
.C o,pDPT , j
*f pp.* DDE \
S$9 PP* DpD 1
f Aldrih ' 7 Dieldrin
1
i
41 \. ^.
WATER PCB-SD0000056593
c c-
V. Effect on Monsanto
worldwide basis:
Plasticizers
Total/Tear
jm ibs.
34H lbs.
lOffi lbs.
$16ff G.P
*
$2-3* G.P.
pm
$8llH G.P
Already competition is using certain data against us in competitive
situations.
._
`
A. Legal Liability
Direct lawsuits are possible. The materials are already present in
nature having done their "alleged damage". All customers using thes
products have not beei officially notified about known effects nor c
our labels carry this information. These are only a few of the
possible legal implications which would best be covered by the
legal department.
B. Public Image
The corporate image of Monsanto as a responsible member of the
business world genuinely concerned with the welfare of our environ
ment will be adversely affected with increased publicity.
The evidence proving the persistence of these compounds and their universal presence as residues in the environment is beyond questioning. This combined with certain scare publications is cert to give an adverse image. Guilty^association (with DDT) will pre
vail as the background while actual facts may be sparse.
'
C. Customer Relations
STR QZ1<3^
Some customers who presently use these materials will be "scared of
. to other competitive products. Products associated with the same
.m: ~ .
name or "trademark" will be adversely affected ie., Therminol,
Pydraul and Aroclor. Competitors will use the information for -an
WATER PCB-SD0000056594
(" - 6 - r
. Influence on Monsanto products.
Customers Kill seek other "outs" rather than become involved. VI, Effect on Customers and Ultimate Consumers ~~ One of the unique features of PGB's is their fire resistance. Here the
basic decision whether to risk lives due to fire or risk extinction cf, some species of birds. In this case the PCB would probably be accepted as a necessary pollutant and tolerated under controller conditions.
A. Electrical Industry - Capacitors and Transformers use Aroclor
because it is the best inexpensive dielectric fluid available.
B. Pood Processing - Bulk "deep frying" units for potato chips, fish,
. and doughnuts use the fire resistance fluid as an indirect heating
medium.
'
C. Die Caster -- and other hot metal working industries fire resistance
fluids to protect the worker^
Affects a wide range of plasties and adhesives because the PCB
serves as'the plasticizer.
A wide range of paints and coatings are affected. The "Carbonless" carbon paper used so widely would disappear. 7H. Involvement With Other Producers Although Monsanto is most probably responsible for the U.S. contaminati and Jointly responsible with MCL for .the United Kingdom problem, we cannot accept responsibility for the world. There are five known producers in the free world, several possible producers behind the iror curtain and couple of additional companies making overtures about entering the business. Monsanto representatives have on one occasion discussed this problem with a couple of these producers but.they expressed no great concern. In fact. It is highly possible that one o
~ SIR 021947
WATER PCB-SD0000056595
-7 -
these manufacturers Is dumping his waste Into the Rhine River. Certain! any action taken by one producer will most assuredly affect the other. :T .It Is entirely possible that a Joint plan of action could be developed 'but will most probably have to be spearheaded by Monsanto. It is also lively that producers of other chlorinated products used with PCB's will be dragged into the investigation. '
TUI. Sources of Contamination
'
Although there may be some soil and air contamination Involved, by far
the most critical problem at present is water contamination. To our
knowledge to date the contamination can be broken down into two general
.categories, open and indirect pollution.
A. Open Pollution - Our manufacturing facilities sewered a sizeable
quantity of PCB's in a years time.
'
1. Fluids
Fluids are probably the most open source of pollution because c
their mobility. They also may be the least serious because the
are generally the lower chlorinated materials.
2. Electrical
.
Electrical customers have in the past sewered their wastes.
3. Heat Transfer
Heat transfer customers have sewered their objectionable and
their spilled material. -Industrial
These fluids have generally been sprayed into drains, washed
down sewers and generally regarded as very harmless. |W 5*
All of the fluids have had the "piste constituent dumped on dirt roads
a "dedusting agent which inadvertently found its way back to the stream.
STR 021*548 WATER PCB-SD0000056596
-8-
c.
( 5? Plastics
: ' " 'The plasties are net as mobile as the fluids so therefore they
\ have net found and cannot find their way back to streams in op
-- -- . pollution.,
'
B. Indirect
`
Shipping containers and the cleaning thereof for subsequent use a source of contamination)
1. Fluids
a. Electrical - Disposal of "burned out" transformer and
capacitors may find its way back to streams. Scrap units
(new) are generally disposed of in land fills but could
possibly get back to the stream.
''
. b. Heat Transfer ~ Leaks could contaminate,
e. Industrial - Cross product contamination carried out of a;
air compressor. Residual material carried on parts.
2. Plasticizers
a. Process Contamination fro Washing
(1.) Environment Contamination
Swimming pool paints
Incineration of war coatings
'"
Traffic paints
' (2.) Product Contamination
STR 021949
Coating for tank lining S&&:i&ng' inks and paper coatings
Certain adhesives
T*??. IX* Recent Technical Changes Which Have Bearing m the Contamination '
' AFluids
- The sources of pollution were pointed out as they have been in t:
past because we are dealing with that quantity of material in th-
WATER PCB-SD0000056597
f -9 -
environment today which was deposited over the past forty years. We jsue^must state that res? ponsible people throughout the industry have taken
.corrective action to reduce contamination in the last two years. There -------have also been technical advances which have brought about the use of
lower chlorinated biphenyls which may be an advantage because to date t low chlorinated ones have not been identified present in nature. 1. Electrical - The large customers have established collect systems a
the waste is recovered. Incinerators are being investigated and . built for the disposal of the materials. There has been a shift
away from the higher chlorinated types products and could probably shift almost entirely away from those products. 2. Heat Transfer - System have been tightened up and redesigned to . .confine the contents Here^to^* the trend has been to shift away
from the higher chlorinated materials. 3. Industrial - Sealing ponds have been built by the large manufactur*
. to catch the material and decant off the PCS for reprocessing. Thf
trend here as the other fluid areas has been towards the lower
chlorinated materials.
.
4. Plants - The plants effluent has been passed through limestone whi
provides surface to catch some of the material. But high concen
trations can be found in our effluent (that is relative to those
findings in nature causing the problem).
B. Plasticizer
Quite opposite to fluids the trend in plasticizer Aroclor has been to
higher chlorinated biphenyls. In plasticizers the lower chlorinated
biphenyl will not be an acceptable solution however, the lower chlorir
terphenyl-c-cculd offer a possible solution.
.
STR 021950
WATER PCB-SD0000056598
fc
r X. Courses of Action A* Do Nothing
10 r.
" e cannot deny the findings and the acquisitions by the various
.......... ............ .. agencies. If we took no action we would likely face numerous suits.
Ve would' let government tolerances be based on public and
political pressure along with any experimental or developed data
which they may generate. We would most likely be forced out of
this business. Other product areas would be adversely affected-r
We would project an Image as an Irresponsible member of the business
world. Project poor customer relations. The only advantage to this
technique offers is it reduces the cost but this too must be
weighed against potential loss of business.
B. Discontinue Manufacture of All Polychlorinated 3iphenyls (PCS)
Although we all realize this could be an eventually unfortunately
the solution is not this simple-' Assuming we did step manufacture
immediately, the pollutants are present in the environment,' the
liability is present and possibly by the shift! to the lower
chlorinated materials and the recovery techniques the contamination
may already be reduced to an acceptable level. Obviously the entire
business would be lost without any or very few substitutes to be
offered, other product areas would be affected. Financial loss
could be considered due to raw material contracts, customer contract
and royalty -- secrecy contracts. Competition would take advantage
on all fronts. We would be admitting guilt by our actions. Loss
of capitol investment in the plant, associated utilities, and asso
ciated processes. We would possibly gain a little public image on
this action*
STR Q219SI
C. Respond responsibly, admitting that there is growing evidence of
environmental contamination by the higher chlorinated biphenyls and
take action as new data is generated to correct the problem.
WATER PCB-SD0000056599
11
This approach would enable us to phase out the higher chlorinated
materials' In many applications where they are iso longer necessary
_ ,r really desired* Weeeuld maximize the corporate image by
publicizing this act. Ve would reduce a known pollutant*
> ^
.... .................
.
* ..
Additionally we could gain precious time needed to develop new
products and investigate further the- lower chlorinated materials.
As new research data is generated our course may be altered
considerably. Certain limited actions may reduce or limit the
problem.
STR 021952 WATER PCB-SD0000056600
12 r
XT- Recommended Course of Action ; ' Based .on the information available today the only recommendation we can
honestly make is respond responsibly admitting that there is growing -........; evidence of environmental contamination by the higher chlorinated
biphenyls and take action as new data is generated to correct the problem.
XU. Implementation of the Recommended Course of Action
A. Immediate (By 12-1-69)
' 1. Set up a task force under a project manager or the equivalent
. responsible for initiating, directing and implementing all actior
that Monsanto decides to take. This includes sufficient budget
necessary to cope with the immediate problems. This task force
. should Include representatives from Medical, Legal, Research
. and the two involved Marketing Groups and Public Relations and
must conduct liaison with MCL and other locations Involved in
the problem.
2. Decide on timing and content of any public and/or customer notif;
cation of PCS problem.
B. Interim (Within 3 months)
Fluids
Plasticizers
1. Confirm Arocler 1254/Aroclor 1260 are found in the envi ronment.
1. Announce differential between fluids/plasticizer uses.
2. Publicise the difficult anal, 2. Announce safety of other PCS';
tasks.
.
chlorinated terphenyl. .
3* Protect other PCB/chl. terph. 3. Educate customers on. control < effluent for all products.
4. Announce plans to reformulate 4. Initiate program to develop- A,
certain Themlnols and Pydraul
1254 & 1260 substitutes
. where control of the product
is difficult.
.
SIR 021^53
WATER PCB-SD0000056601
r
'
c
5.
6. __
Emphasize better control over 5 Investigate 'with manuTacturan
other Aroclor 1254 & 1260
the feasibility of alternate",
uses.
;
products.
Initiate' customer education or Gs--taadyee--242 need for effluent control of
aU products.
7. Determine composition of aU FCB's.
Develop a comprehensive Program
0. Short Term (within the next 12 months)
1. Research - Expand program for more meaningful biodegradation
Medical .
.
studies and confirming analytical results. Expand
-toxicity studies. Follow developments concerning
publicity and those developments covering political
implications of PCB contamination.
..
2. Marketing - Discontinue or substitute replacement products for
` those applications of Aroclors 3254 and 1260 where the Aroclor
remains mobile.
Work with customers to clean up plants on other Aroclors.
Report the habitual violators or "do nothings" to the product
group.
.
Reclaim or safely dispose of fluids.'
STR 021954
Consider renaming products that do not contain PCS. Follow ar.d report market developments such as customer disposal systems. Follow and report any political or public feedback which,may affect the contamination problems and must be coordinated with Medical, Research and Legal.' ' 3* Production - Clean up plants and stop gross contamination. 4. Legal - Define our present position, recommend reasonable aeti' that will not unduely alarm the market but reduce the exposure in terms of liability. Coordinate recommendations with
WATER PCB-SD0000056602
rC - 14 -
5 Public Relations - Publicize actions where believed advantageous
Certainly discussions should be held with other producers withir
sane period to determine their planned course of action, if any.
D, "Long Range Tentative Outline (Prom 1 year to 3 years)
Realizing that the comprehensive program must be outlined the "Long
Range Tentative Outline" is meant to serve as a guides All aspects `A
of this program should review quarterly by Organic Management.
1. Research-Medical
' Continue biodegradation studies and analytical support
Isomer distribution
Toxicity and metabolism studies
` Water soluble removal
Incineration analytical support Confirmation analytical
.e
`
- Contract academic research for reference
"
Develop new and improved formulations
2. Manufacturing
a. Process Research and Development
(1.) Identification of typical Aroclor isomers
(2.) Develop control for effluent composition
(3.) Test substitute formulations, etc.
(4.) Develop new processes
b. Clean Up Plants
.
c. Modify processes to meet market heeds
,,
3* Engineering
_
a. Develop and set up on plant locations incineration systems
b* Design new processing equipment as necessary *
4. Marketing a. Specify alternates or changes
b. Customer-liaison
021955
WATER PCB-SD0000056603
r - 15 -
. e Set reclaim or disposal of fluids
, r
d Work on name association problems
*
5. Patent
........... ..
Investigate trademarks registered
Cover with patents any work felt patentable
6. Environmental Control
Develop cheap disposal systems for customers
a. Incineration or pyrolysis
b. "Biodegradation unit etc.
-
c. Consultants in pollution control
' 7. legal
_ Investigate and define our position.on Royalty secrecy
' agreements.
Contracts - Raw Material and Customer 8. Public Relations '
Portray to public positive actions at correcting the contamination problem. Release periodical statements covering our position.
mi. Probability of Success
.
STR Q21fS4 WATER PCB-SD0000056604
- 16 -
(
XIV. Cost of Program
Neither the program nor the costs have been clearly defined at this tic
However, a cost estimate of $220,000 for toxicological work alone has
been presented. Tentative figures Indicated under the worst condition:
the entire program could run as high as $2.0-2.5H. At this stage it i:
very difficult if not impossible to develop a reasonable cost figure bt
one point is clear it will be larger than the normal research budget c<
handle. For this reason, assuming the approach is acceptable, we shai:
. be forced to ask for additional appropriations to fund the program.
XV. Future
Follow developments on the problem as they unfold.
Develop an aggressive research program to confirm or deny findings and
better understand the problem.
Develop costs for the duplamentation of the Recommended course of
action.
' `
Develop specific actions with each department involved
Submit the actions with costs for approval
Develop a timetable to solve the overall problem.
Prepare for "precipitious pullout" or drastic legislative action althc
we do not feel this is & likely possibility.
STR 021^57 WATER PCB-SD0000056605
,CTIQK DO HOTHINa
DOLLARS
r ROPIT ADD LIABILITY VS.
DISCONTINUE MANUFACTURE DF PCS
------------------------- ,------------------------ 1------------------------1---------- ;-------- r-r
. 70 71 72
...
.. ,
* Tin /
.
73 .
..
'
DOLLARS
RESPONSIBLE
APPROACk
DOLLARS
i .70
'
j------------------------r------------------ r~
71 .
72 73
TSsse- * 1
'
WATER PCB-SD0000056606
PROFITS
c c:
PROBABILITY OP SUCCESS ;
Time
STR 021959 WATER PCB-SD0000056607
fRotfr (run UP/61UTY. vjlTiv.L WATER PCB-SD0000056608
T96T20 MIS
i$
WATER PCB-SD0000056609
I
i Monsanto
IW
TO
O
y. B. Richard - Research Center
September 9 19^9
-
DyErFrEnNnSEroO--F AROCLOR r
3 ?, Hodges.
PHOBG
So Wheeler - EOTS
Qenenl Policy .
e'
Make the Oovt., States and Universities prove their ease,
but avoid as much confrontation as possible. Comply and */| work with public officials to meet or" exceed requirements
ahead of time. .Adverse publicity and competition are
the real weapons.
.
Analytical fin Air 1 - Which Aroclors are present? Where?*)
for Aroclor lln Water- Which compounds-^ . .. (in Animals ^interfere?
ig J Ag
Keep track of how much contamination - which sources.
Prove Bloharmful - Let Oovt. prove its case, on case by case
Monsanto Vi sit-Oovt, Biolabs - in search of toxicologi
r
experiments and evidenc vs. Aroclors to keep up
. progress.
Monsanto Prove Bloharmless - Limited work at Ind. Bio-test -
"Safe" toxic fm&n level for < mammals via
1 fish
Rats Chickens
Pish'
Seek evidence of Bit
d<
Question evidence a<
u:
Question shrimp toxic
especially other t<
chemicals.
If Aroclor bad, ott
must be worse.
Probable Outcome
Ve can prove some things are OK at low concentration.
Clive Monsanto some defense.
..
We can't defend vs. everything. ' Some animals or fish or
insects will be harmed.
.
Aroclor degradation rate will be slow. Tough to defend
-gainst. Higher chlorination compounds will be worse
iover chlorine compounds.
,, ,
,,
\lH
Therefore we will have to restrict uses and clean-up as
1much3s -Mg-can, starting immediately.
PLAINTIFF'S
t EXHIBIT :
C\/ Q "7 / MON 0209
I
WATER PCB-SD0000056610
<J 3
Therefore ip will have to work for alternate product! in end us# applications; for Aroclor production facilities.
Cleaa trp Arodors and substitute products where necessary
sad Wncn required. berdreTSfrata f
publicity snd competitive activity over.
whelm a
" ... .....
Water Pollution seems to be first Issue
Aroclor product is refractive, will settle out on solids sewerage sludge * river buttons, and apparently has a long life.
Florida or gulf Coast - Aroclor 1254 - Aroclor 1260 pres< Issue.
40-200 ppb - causing problem at Pensacola (Monsanto) In plant effluent -causing " with shrimp.
- can't risk shut-down of plant.
Federal and State can extrapolate to other plants In . Gulf area.
San Francisco - Aroclor 1254 and 126 .
leported iroclor to be present In San FTaneiaee lap.
leported to be thin egg shells In birds
- Lot of screaming -
.
Great Lakes Warf studies on BBT . Aroclor 1254 will be found*
Aroclor 1242 Will be found?
Air Pollution - Possible spread - but less of an Issue
' right now.
Analytical work mere difficult.
*
' '
Direct Contact with Product
Doesn't seem to be an Issue - except for food heat transfer
I
Ve don't believe Aroclor Is being used as carrier for /
Insecticide - sprayed around -
, .
.*
.
*. *
>/.
iI !* i
Ve are not positive but most uses are "closed" systems!! ..
or products used In solid plasties, or adhesives, or S* J"'
sealants. . .. .
J*r ;*
'
MON 0210 4 0079 WATER PCB-SD0000056611
F. fluid
`
Product
-
Hydraulic fluid '
Mr Compressor fluids Hast Transfer: ' Capacitor fluid
Transformer fluids
Possible Pollution by
Possible j
easterners Plant Operation by Customs
Its leakage external
Iiii luki| external 3es, leakage external Tes, leakage frcm plant
- Scrap materials. Vo, Should be clean. Tes, Reworked trans formers
Possible Johnson. Hot
Castings.
Leakage int
Leakage int
In produet closed for < In product 1 closed for <
Capacitors can go to land fill dumps. Probably not burned, in A1 containers.
** Need t take care of Aroclor In discarded transformers. Product could be drained and reworked.
Probable Conclusion
Hydrasslie .Leakage
. ' * sMr. Compressor fluids
Hydraulic fluids ` ;
Product could be assist at machine but will take a lot of clean-up work with customers. 111 have to haw replacement product - with less-sensitive components. Work from this base on clean-up to prevent more pollution problems.
Must expect "shrimp* experiments. Vest Florida State, to be "aired" sometime toons next few months.
This will lead to bad publicity
and competitive action vs. all
Pydrsuls. .. .
' *'
*~
-4 ' .
'# will have to try to confine to
Aroclor 1254 and Aroclor 1260.
/
4 0080 MON 0211
WATER PCB-SD0000056612
O -4-
Vt will have to take action before that time.
Gulf Coast
.
Action V. '
Richard
Fallon/ Richard
Fallon
Be able to replace Aroclor Ifft and Aroclor 1260 in Pydraul AC and 625 in 2 month's time before Nov. 15, 1969.
Have trial product in hands of Gulf Coast accounts and distributore before Dec. 15. Suggest possible buy of "all phosphate" ester from Food Machinery. TJse this as one trial fluid MCS for insurance.
Richard/
Suggest possible substitution of Aroclor 5442 for Aroclor 1254 in hydraulic and compressor blends. E. Wheeler Judges lower order of toxicity and solubility for 5442 series. Have to test product in pump test for deposits.
Fallon/ Suggest field trials of our own all-phosphate Richard ester.
Fallon/ Xuhn/ Kountz
Work with large customers to clean-up streams. Bring in Findett as mfg. partner in the recycle business. Get money out of recycle operations.
Inland-Waterways-
Wheeler/ Be close enough to Great Lakes studies to Judge Richard situation. Are there animals which are being
affected by the concentrations found?
Richard
Be prepared to replace Aroclor 1254 and Aroclor 1260 in 4 months in hydraulic fluids and in air compressor fluids.
Richard
Be prepared to replace all Aroclor 1242 or 124f in 6 months in hydraulic fluids. This means replacement of Pydraul 312 series, and control of sale of Aroclor 1248 to other hydraulic accounts such as Cities Service and Mobil.
Heat Transfer
0061
Fallon/ Systems will have some leakage depending strongly
Roush/ on engineering and maintenance. Need to work
Kountz with customers on clean-up,
.
Fallon/ Roush
Need to replace FR especially in food or sens!siv
product arses
the product is getting
into water. Sec di-sh washer eompounds. S5-ee
letter Z. Wheeler to J`. Fallon.
0 \ V'i
(>t VI!
We have possible rep cement products in Thermir.:\
mom
to
Therrr.ir.-
WATER PCB-SD0000056613
o -5- D
Action Kuhn `
Kuhn/ Fallon
Try to assure adequate production of Therminol 66 in fact of decreased Aroclor production. Ha and terphenyl supply nay becone short. Switch customers to Therminol 55 '
or Theninol 66 ahead of pollution problems in customers plant. Work with customers on plant and dumping practices. Flndett already set up to rework. Need to make them a manufacturing arm. Ve get sale of recycle-rework fluid.-
Capacitor Capacitor plants have re
Fluids
purification and recycle
systems but up to 5* of
product can be lost by
poor plant producers and
off-quality material.
ICkt. Benignus/
Bryant
5% of production could be
Eng, -Keuntz/ Mfg-Hodges .
HT lbs/year. This is a big loss for the type of pollution we are trying now
to guard against.
_
Capacitor products
Enclosed in A1 or stainless steel for 5 to 25 year period. Will ultimately have to dispose of capacl tor products.
Recommend we try to save this product fo a time.
Action Eng.,TSDPlant Pol lution Con trol Hodges/ Kountz
Monsanto must start to work with capacitor people to clean up plant practices. Ve have set-up to accept material for rework into . hydraulic fluid but this relocation is not a eatlsfactory solution. Material must be reworked to electri cal grade or destroyed, whichever is more economical. Must start now to get con trol of off-grade material.
Recommend replaeeaen future Aroclor buain with other products. Have 2 years.
Action
Monsanto must help plant clean- *'
up of customer plants decantation,-
coalescing, adsorption, dls-
posal of adsorbent or recycle of
adsorbents.
._
Monsanto badly needs "know-how*
for clean-up.
Monsanto should seek Qovt. contract money for clean-up research, (See MRC R. Binning, B. Nelson)
h 0082
WATER PCB-SD0000056614
Transformers
Action Benign**/ ` Bryant
Traniforatr Plant can operate
In a clean, efficient manner
with recycle of off-grade
Aroclor.
.
Should advise disposal of
filter element material* so
as to minimize chance of
water pollution. Incinerate
'or dispose.
.
Reworked transformers pose a threat if the Aroclor is ' dumped into a water stream.
Product transfer?. can remain close; no exposure for < Should try to ret business by clear, by education of c tomers.
Action Benignus/ Bryant
Should try to minimize chance of dumping "old" fluid by re working and by educating co. shops and collecting product for rework or disposal.
Dalton is set up in England
to rework electrical grade
fluid.
.` -
Kuhn/fcountz Need rework facility here *
Pindett?
disposal scheme.
Monsanto Plants
The Dept, of Interior and/or State authorities could monitor plant outfall and find ppm of chlorinated biphenyls at Krummrich or Anniston anytime they choose to do so. This would shut us down depending on what plants or animals they choose to find harmed.
Action - Take steps to see that every precaution is taken
to prevent Aroclor entering water streams. Try
to reduce to ppb level.
.
1
P.Hodges-Seek a Govt, contract on adsorption and incineration
TSD cycles - MRC.
.
Engrg.-
.
.
Eountz . Take samples of streams and river water and mud
. evidence for before and after clean-up. * Samples
' can be stored for further analysis if we* can* t
- keep up current with analytical determinations.
*
-
Apply Monsanto clean-up method* to customer plant
, ele*a up
and procedure*.
.
4 0083 WATER PCB-SD0000056615
Action -
' Bngrg. k Mfg.
. Kountz and
Kuhn
Evaluate liquid incinerator* v*. solids
handling incinerators for disposing of Aroclor
and pentachlorophenol wastes. I estimate
Aroclor disposal at 1-4H lba/year, exclusive
of cleaning up river bottom* or outfall
bottoms.
..
Hydraulics 20% of 4ff lbs Heat Transfer lOJl of 2ff lbs Capacitors '*' 5% of 20ff Transformers 5$ of 15ff .
800.000 lbs 200.000 lbs 1,000,000 lbs 750.000 lbs
2,750,000 lbs
Central
Eng. &
Mfg TSD
Kountz & Kuhn
Possible help from
MRC
Set up an incinerator to handle Aroclor dis-\ }
posal - preferably one which will handle
\
solids such as muds - slurries as well as
;. I
liquids. Have in operation within 12 months. /P *
Ideally have incinerators available different '
sections for disposal.
y
Chronic Toxicity Studies Ind. Bio-Test
Wheeler Keller
Ind.Bio
Test
Continue studies to establish PDA type limits of toxicity on Aroclor 1242, Aroclor 1254 and Aroclor 1260. Rework with R. Keller-S. Tucker the number of samples which are to be analyzed for Aroclor in tissue. Try to see if 'Aroclor are changed metabolically. Does concentration level off, decline if feeding la stopped?
.*
Institute studies against the most limiting
biological parameters. If shrimp are the
most limiting species for Aroclor levels
of toxicity, then we will have to have,
biological studies on these species to eon-
ifirm.\ *o.r d...en.y * a*d.v**'er*.s..e"i*f.'i**n: d..*ing. s . *.7*
; '**-*.
4 0084 WATER PCB-SD0000056616
3
6 8
Biodegradation Studies : "
'
' Set up rate of Biodegradation studies with Znorganle Div. on Aroelor 1242 vs. Aroelor 1254
. ' Aroelor 5442 vs. Aroelor 5460 Swisher Chlorinated diphenyl ether
Chlorinated paraffin vs, ehlorlnated naphthalene * Chlorobromo Aroelora 1242 and 1248
Baxter Contaet Baxter and Lldgett at MCL regularly for results on
Lldgett Aroelor degradation. They are reported to be moving on
MCL laboratory experiments.
Establish contact with ehlorophenol degradation studies
of Cellu-Chea Group.
.
' WRRims
^2-
V. R. Richard
-
4 0065 WATER PCB-SD0000056617
Jirts
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' 4m*mlogmm. wt> tho Voodiah mckt for.Arodw fivo pan< w voald bo fxmtafal if you oool4 arxang
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or paMLeatim of data. 4a Im
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PLAINTIFF'S EXHIBIT
STR 017390
35 Py 10 WATER PCB-SD0000056618
cz: Mr-. D.,~. Carte rtr. - MZ
RISING & 3 X R A N. Q
OP/BO
AKTI S m Q UAGi
3S PWraSJSS* S 44 49
TUi I34.
aAmmamot 7S-4&4&
STOCNMOWM V* SVCAvAdXM 47
November
S p K-c'*
Monsanto Europe
BRUSSELS 3 * Belgium
For the attention of Mr. D. WOOD
Dear David,
re: AECCLQRS
As mentioned, there has been some publicity in Sweden
concerning investigations made at the Institution of
Analytical Chemistry at the Stockholm University. These have revealed that a group of products called yJ* Polychlorinated 31-Phenols - PC3 for short - accumulated " in certain organs o aairnls. They-are said to be related to DDT and equally poisonuous.
The findings were discussed at a meeting of scientists at the Wenner-Gren Centre in Stockholm on November 22. Below please find a translation of an article in the
Swedish daily paper "Dagens Nyheter":-
"It Is found in salmon and In pike. It.is found in
. sea eagle living on fish. It Is found on the^sur-
face of the needles of the fir trees, that is Tin
the air. It is found in the hair ot -a-five months
baby ...
` "5
. v* *..* . *!
The scientists working with biocides have for a?long
time seen this something as unknown "peeks" on /their
gas chromatographs and at a meetingx-4C the Wenner-
Gren Center, Research Assistant Sdren -Jensen of the
Institution for Analytical Chemistry at the Stock
holm University could reveal the Identity of these
peeks. It has been found that they consist of a
group of poisons. Polychlorinated BiahanoXs. (for
short ?C3) which are closely relaCaSTTc, and equally
poisonous as, DDT.
PC3 is broken down considerably slower than DDT and gives rise to damagyof liver and skin. PC3 is not
STR C17391
r-- \ / 4 A
WATER PCB-SD0000056619
^ f 3 I ^ & 5TW fH
ME5A, Brussels - Mr. D-. W(
used as a herbicide*
Itr Is; not; manufactured. In-
Sweden but Is supposed to used by the Industry" to
quit some extent-. No special industry 'can, ao. fan
be accused of b&ln^_vhe^^ugc^o^l^^naial'jAt:f, on. `
Research Asst. 2. Jensen has tested 200 fishes and
a number of birds Be has taken, several samples of
air and has reached the conclusion, that PCS Is
equally cannon, in Nature as chlorinated hydrocarbansof the type of DOT, DDE, and Lindane. Even, fish in
Ladd4assure in Lapland contain PCS. Mr. Jensen has. also found that ?C3 does not appear in animals living on a vegetarian diet, such as the elk.
In the course of his work, Mr. Jensen has not found anything indicating that the source of contamina tion comes from agricultural additives. It is, however, obvious already now that PCS is most
frequently found in organisms living in water or feeding frets water animals. In all examined pikes
PCS was found. In a sea eagle found dead outside Stockholm it was found that the liver contained .10 mg of mercury ter kilo. 76 mg PET and consider ably more PCS. The exact figure has not yet been
"determined.
PCS is found in water and in air, ar.d not only in the Swedish air, but also in e.g. London air. Mr. Jensea has not yet been in London for sampling but could identify the poison by studying a gas ehraHstcfffam of air published in a British techni cal leumsX.
X Mr. Jensen har also examined the hair of his family and himself and has found PC3 on all samples. Most PC3 was found in. the hair of his wife but most sensational was that the girl aged 5 months bad. more PC3 in her hair than her brothers and sisters of 3 and 6 years. Probably the girl had got the poison via the mother's milk.
In the State Museum Mr. Jensen has examined the.
whole collection of sea eagles dating back to i860. By testing It could be established taat ?C3 was present only in birds from 19^4 and thereafter while birds collected before 19^ were quite free from PC3.
The us of PC3 in Sweden is net established in detail. According to American sources these types of products are used in the manufacture of a variety of heatresistant material. They are used for electrical insulation, for fire-proof heat transport in hydraulic oils, in lubricating oils used at high
STR 017392
WATER PCB-SD0000056620
I s > (I ^ S. JT * N 2
temperature and pressure*, in pain-ps: and; as- pig ments in various plastics* PC3 is not- imported; only as such. It is also part of several* finishedproducts. Nothing is known as to the way in which it reaches the water and the air. According toMr. Jensen* products containing PCH should have this openly declared.
PCS is equally harmful whether absorbed via the. skin* through the food* or by inhalation. In con tact with the skin it can cause dema.. For DDT" the highest permissible concentration in the air has been set at 0.5 - 1 mg/eu.metre. For PC3 it has been mentioned to be 0.5 mg/cu.metre. Mr. Jensen will now try to get more complete analytical material. He hopes eventually to be able to disclose the source of the contamination and will also increase his cooperation, with toxocologists and geneologists."
Another daily paper, Svenska Dagbladet* has & similar article. Here It is mentioned that Mr. Jensen*, work ing under Lab orator (Professor) Gunnar Widmark* hasdisclosed facts which will have far-reaching- importance since the findings have proved a new source of pollu tion of the nature.
One of the participants at the meeting was Dr. A.V. Hcldea of Scotland* scientific contact man between the twelve a.H.C.B. countries* who has established coordinated analysis of chemicals used and found in nature.
I suppose there is no doubt that what has been termed Polychlorinated Biphenyls is equal to Arcelor. There is also no doubt that the published facts will cause considerable unrest in several quarters. We probably will have to have Aroclor registered with the Swedish Board of Poisonous Substances and the industry will have t be particularly careful in handling the material. The problem in some eases of course may be the disposal of used material. I understand that there hardly exists a convenient method of destroying Aroclor and that possibly burying unuseable material may be the only answer.
We shall be glad to hear from you soon.
Yours sincerely
1
WATER PCB-SD0000056621
INDUSTRIAL HYGIENE AND TOXICOLOGY
'XOLVUZ 19
SEPTEMBER, 1937
Number 7
-V THE PROBLEM OF POSSIBLE SYSTEMIC EFFECTS FROM
L CERTAIN CHLORINATED HYDROCARBONS*
m'.,CkcHi K. Drinker, Madeleine Field Warren and Granville A.
\If?c/ ' ' Bennett
''Prpmiment of Physiology, Harvard School of Public Health and Department of Pathology, . Harvard Medical School, Boston, Mass.
;T-.
HE use of chlorinated naphtha rapidly and thoroughly as possible.!
Tlenes and compounds of allied pharmacological possibilities is
In brief these cases were as follows: Patient 1. Male, age 21. The previous
; ntremely wide, and with the stemadeydical history of this man was in no way
growth of the use of electricity is cer- significant except for the fact that he had
':;.tain to expand much farther. For an attack of jaundice about 6 weeks prior to
;; years it has been known that many of .these compounds cause a troublesome f.seae, and there is a large literature
his fatal illness. Late in December, 1930, he became badly constipated and had much abdominal pain and distention. When ad mitted to the hospital he was slightly jaun
; #pon this phase of the subject. Our diced and was evidently very ill. He was
~"fave8tigations have not been concerned somewhat anemic and his skin, particularly
ith chloracne but with the possibility ;fif systemic effects following ingestion
inhalation of such products. In the
upon the arms, face, chest and back, showed many pustules. He died after a brief period in the hospital, and at autopsy was found to
v *fs*nG f 193G, the Halowax Corpora-
t The Halowax Company makes many
*mi a division of the Bakclitc Cor-
produrts besides chlorinated naphthalenes, and it has conic to our knowledge that all of
fttion, called our attention to three these products arc indiscriminately called
_
esses of jaundice in workmen
"halowaxes" by purchasers and users, and are lumped together as possible causers of
jt^ng chlorinated naphthalenes and acne and even of svstemic disease. Since
Chlorinated diphenyl, and requested "halowax" is merely a trade designation, care should be taken to describe compounds
the subject be invest mated as by their chcmicnl names and thus avoid
condemnations which are both troublesome
Received for publication June 30, 1937. and misleading.
'
'3i 2R3
'.ii
i ;
EXHIBIT
^79
904313 WATER PCB-SD0000056622
a: s* y . Ii .
Hr-. *
- i-
.i
ji . : iB.; i
jfT- !
JOURNAL OF INDUSTRIAL HY
have a cirrhosis of the liver with acute yel low atrophy superimposed upon it. This man had been exposed to low concentrations of vapors arising from a mixture of tetra and pentachlornaphthalenes, together with approximately 10 per cent of a refined chlo rinated diphenyl. While both he and others * engaged in the same work had chloracne, there were no other disturbances of health in fellow workmen, nor was there any pre cipitating cause for the acute yellow atro phy such as treatment with arsphenamine or exposure to dangerous concentrations of carbon tetrachloride.
Patient t. This was a young man who died in February, 1936, after an acute illness characterized by jaundice. He had been exposed to fumes arising from a mixture of penta and hexachlornaphthalenes. There is no record of chloracne. The patient worked with a large number of other people of whom but one (Patient 3), a close friend, had significant illness.
Patient S. Another young man employed with Patient 2. He became jaundiced in March, 1936, and died after an illness of 2 weeks. A careful autopsy resulted in a diagnosis of acute yellow atrophy of the liver Here again no history could be ob tained as to a precipitating cause, and there was no record of preceding attacks of jaundice.
In addition to these three very re
cent fatalities, we have learned of four
other possible cases, none of them
fatal. All of these have had jaundice
and the entire group consists of iso
lated individuals who have been picked
out of large groups having the same
exposure. In but one instance, Pa
tient 1, is there record of antecedent
disturbance of health, and the general
health of fellow workers has been good.
Such cases have not been reported
in the medical literature and only occa
sionally can one find reference to sys
temic effects of any sort. For exam
ple, Courtois-Sufiit (1934) reports on
work done by Touraine and his asso
ciates (1931) who examined (if) workers
who had been exposed to trichl^
naphthalene. Of these 13 were fomjt to have mild digestive complaio^^
anorexia, nausea and vertigo, Courtois-Suffit remarks finally,
^
sorption is certainly possible and
have for proof of it some of the digt^fj
tivc and general complaints wh *
have been due to it. But they app
to be of little consequence consider^ the mildness of the digestive troubled
and the absence of respiratory p}^ nomena."
In Tourainc's cases the exposure**to a trichlornaphthalene, whereas th*|j
American cases of acute yellow atrophy;? were exposed to compounds of higher^ chlorination. Our own experiment*^
indicate that trichlornaphthalenes i quire enormous dosage, far beyo anything encountered in industry, order to produce liver damage. Teffij eky (1927) reported a number of casstg of chloracne in persons exposed to* chlorinated naphthalenes with a chlo^ rine content ranging from 14 to 53 perj| cent. He found that the lower ths chlorine content the less the acneA Mittelstiidt (1935) examined a numberJj of cases of chloracne due to trichlor*^ naphthalene and reported a number vague general complaints but nothin| 3 in the nature of serious disease. Kfr-S garding his animal experimentation, A
Lehmann (1919) reported that nniVg mals fed chlorinated naphthalenes rev fused to eat after a time and that,*,
whether poisoned by inhalation or feeding, at death showed "peculiar"
lesions in the liver. Flinn and Jarvik (1931!) gave subcutaneous injectionsflfv,
enormous doses of chlorinated napb*j| thalenes dissolved in paraffin oil t<T|
rabbits. The compounds used as follows:
j .\ mixture ` ` naphthalene.
2 A mixture of ' ' chlornaphthi
3 A mixture of chlornaphth:
I,, add*ion, sublii : p) were collected i ^jabcutaneously. None of the anim ' sublimate from
after 2 months were
autopsied. The fir Bials receiving (3) o day and the last di< Those receiving the writ* even more Autopsy in these ^striking changes r described, entinT If.'T'Vute yellow atro] fUggestive to eausi dude that "eertai thalenes or impn
them are callable atrophy of the live
At the beginn Flinn and Jarvik fact that then- h, of acute yellow ; in men working w thalenes but give to them. These c the same as tin beginning of this . Cue may sun literature tqion : these substances
1. With the e tion of acute yi I wul Jarvik (1931 or even suggest] upm human heii
2. There is e\ that the degree
; tfl * i , ' ,
BiHNiH
WATER PCB-SD0000056623
M r|
or CIU.OUINATKI) riVI)l{Or.VI{IU)\S
2,So
1/1
irei as I
W,t 7,1
4 mixture of tri and tetrachlor-
naphthalene*.
A mixture of tetra and penta-
""" chlornaphthalene.
uK%. A mixture of penta and hexachloniaphthalcne.
'l addition, sublimates from (2) and
Vere collected in oil and injected
fpcutnneously.
.
^Noneof the animals receiving (1) or
Jrti* sublimate from (2) died, and even
fi lftcr 2 months were quite normal when
^'sotopsied. The first death in the ani-
;^ah receiving (3) occurred on the 12th
Isyand the host died on the 2(ith day.
Those receiving the sublimate from (3)
even more severely affected.
^/'Autopsy in these animals revealed
striking changes in the liver, not, as
^4orribed, entirely characteristic of finite yellow atrophy hut sufficiently
Wjtgestive to cause the authors to noti
fy dode that "certain chlorinated naph-
y.lhalcnes or impurities contained in
are capable of producing yellow
FT.Jtlrophy of the liver in the rabbit.''
^ the beginning of their paper,
H^FEnn and Jarvik (193(5) mention tin*
that there have been three cases
,M acute yellow atrophy of the liver
s/?; men working with chlorinated napli2>*'4halenes but give no details in regard
to them. These tuses are undoubtedly
samp those described in the ^vir^nn'nR of this paper.
ma^
the meagre
j~era*uro upon systemic elTeets from
' dTM*0 -^bstanees as follows: h With the exception of the men-
^ of acute yellow atrophy by Flint! Narvik (!93li) there are no reports
v-'W CVcn s>lgge.-t ions of -erions elfeet-
^" . human beings.
T,ll',(' is evidence ((TTeelleekkyv,. til'. fe .lhat the degree of lorination i-
nifieant in relation to the production of acne. In the work of Flinn and Jarvik (193(1) the compounds produc ing serious liver injury were the most highly chlorinated of those tested, though the chlorine contents as given by analysis vary surprisingly little.
3. There are no published figures upon the amounts of various chlorin ated naphthalenes in the air which will produce injury of any sort, and while the work of Lehmann (1919) and of Flinn and Jarvik (193(1) point to the liver as a possible site of injury this indication rests upon such extreme dosage as to fail to apply directly to human exposure.
Kxckiu.mkntai. Wouk
In appraising the possible toxicity of
any substance met in industry it is
first necessary to determine the prin
cipal route of absorption. In the ease
of tin; compounds under consideration
there can be no doubt that inhalation
is their chief means of entering the
body. They are used hot in a great
variety of operations and volatilize in
varied degree. They are often applied
in solution in such volatile solvents :is
carbon tetrachloride and toluene. The
amounts reaching the air under such
circumstances are hardly delectable.
It will however lie shown that- carbon
tetrachloride adds to the toxicity of
the chlorinated napht halenes and allied
compounds, and if there is possibility
ot inhaling these compounds in other
parts of the factory then inhalation of
carbon tetrachloride adds a decided
hazard, Tinier siudi circumstance:
solvent.- such : toluene should In
U'Cil.
( It i~or\ at ion
i number o plants
causes O' to
that even though
.t* - *lFy1
i`.7H ' l&r
904315
WATER PCB-SD0000056624
2Mi .KM'liNAI. OF IN I)('STIt IA (, MVCilKNK AND TON l( 'OI.I HI V
'1.17
rol.
1.1- I
workmen may lie extremely dirty ami careless, rum para lively little of tlie-c waxes is eaten. They are tenacious substances, insoluble in water, and if they get on the hands they stick there, and are not transferred to the food.
Skin absorption is the third possible means of entering the body. It may
lion. They thrive upon a diet \orv similar to man, and in t be ease of tlu-se chlorinated compounds it is possible that diet may be very significant. Finally, their normal characteristics1 have been described so well as to make , the detection of abnormalities both, easy and certain.
ing the end ot (In nictcr was placed it the flow of air in < ti could be adjusted a from a calibratim deflector placed at . pipe into the box \ jure ft uniform d
occur but at best must be slight when compared to the steady inhalation of finely divided or gaseous material in the air.
Method of exposure. -The inhalation experiments were carried mil in four large air-tight wooden boxes, each capable of holding ten rat cages, size
stream of air to tin At the opposin' i
outflow eiid --the was exhausted thn fitted with a dampi
a large central e.xh
if About 4 inches f> the 7-inch pipe inti
of the substances
dneed into the k
cially designed i
(figure 4), 7] inch
^diameter of U in
hold the heated v
were made with a
C-. ` that extruded to
top of the flask w.
"this fitted a short
length. This -hot
into a large rubhei
tightly into a hole
pipe on the umler -
flask in turn was '
'm. 1. Front view amt inflow oml of two lioxes with rat rages in plarc anil doors o|m ii.
heater made to i
below die >ide an
Inhalation experiments are then the most important sources of information, but to them we have added a rerlaiu number of observations upon ingestion and subcutaneous injection of various compounds.
22" .x 22" x M", in two tiers of five
cages each. When the experiment was
not in progress (he doors were opened
wide and the cages kept in place
(figure 1).
At tile center id one end iif each hnX
top. Rubber tu! side arm with a e voir and a gentle through the melt motion and ussttr into each (lask wa*
Iidiidotinii Exp) emu ///.<
Aiiiomls, White rat' have been employed throughout. 'I hey permit the use of a large number o| animals in a relathely -mall inhalation in-i.-iHn-
the inflow end air was introduced through a pipe 7 inches in diameter (figure 2i. I.aeli box was c(|mpp<cd
with an ini|i\i<hi:11 variable-speed elec-
.1 lie blower which blew the air through 'iweral lecl III 7-im-h pipe before enter
centigrade therm kept in place ami time above (lie 7 "'hieh it pa-M-.l tI
Approximately chlorinated uapbi
904316 Eyre
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WATER PCB-SD0000056625
*1. is. " `1 I-.I TK.( TS (IK ('m.UKlN.VH'.ll !l V111!< K All l',( INS
2S7
jpg (lie end "f the box. An orifice pjelor was pluoed in the pipe line, and <hc flow of air in culiic feel per minute took! be adjured and read olT directly (tom a calibration curve. A vane .^deflector placed at tlic entrance of the fTjspc into the box was adjusted to ns ' imrc a uniform distribution of the itreani of air to the two-tiers of capes.
At the opposite end of the box--the y-. outflow end--the air from each box
as exhausted through a 7-ineh pipe fitted with a damper and connected to a large central exhaust fan (figure 3).
About 4 inches from the entrance of the 7-inch pipe into the box, the fumes of the substances listed were intro duced into the inflowing air. Spe cially designed pyrex glass flasks (figure 4), 7| inches long and with a diameter of It inches, were used to hold the heated waxes. These flasks were made with a side arm and tube that extended to the bottom. The -Sv^top of the flask was ground, and into this fitted a short tube It inches in Icncth. This short tube was inserted ^into a large rubber stopper that fitted tightly into a hole cut out of the 7-itieh pipe on the underside (figure 2). The flask in turn was placed in an electric heater made to cover it completely below the side arm and ground glass
tpP- Rubber tubing connected the flde arm with a compressed air reser voir and a gentle stream of air blown through the melted wax kept it in
laotioii and assured uniform heating. Into each flask was inserted a long stem
^tigrade thermometer which was in place and could be read at any
bjne above t|H. 7-iueh pipe through * ih it pa--edd figure 2).
Approximately dO gm. of pulverized
or''t!tted naphthalene- or 20 gm. ol
chlorinated diphenyl were placed in the bottom of each flask and melted in the electric heater. Fresh samples were used every other day, hut it was often found necessary to add 20 gm. of now material even after one run since so much had sublimed. Whatever the ease, the collected sublimate was
Km. 2. Klertrir heater fur maintaining i hlnriiiated ntnpniiinls at a runstant tem|n-r:Utirc in plai-r at inllmv end nf Imx. always removed from the upper part, of the lla-k and a clean top ti.-ed each day. No -ample was ever used for more than two runs.
The lla.-k plus t lie coilt cut - W a-' e;i | efullv weighed at the beginning of the run and at the end, and the lo-- in weight Used to calculate I In- average
I'll!. 3. Outflow end of two Imxcs showing connections to exhaust system.
I'li;. I. I'yrrx gins* lla<k
cause of .slight variations in tin* air flowing
through the boxes anil because0f
deposition of material on the thcr.
mometers and on the inside surfaces of ^
the box, but they cheeked well with
direct determinations through ajr
samples.
Approximately 1 hour was allowed '1
for the wax in the flasks to melt, and j^
come to a constant temperature. At ?
that time the box doors were tightly %
closed, air bubbled through the flasks,
and the blowers turned on. This was
the beginning of the exposure period.
By means of rheostats on t he fans ami
dampers in the outflow pipes, the
amount of air (lowing through the
boxes was adjusted and an attempt
was made to keep the four boxes as
uniform as |Kissible - usually between
llio and 175 e.f.m.
In the first group of experiments the
following substances were tested:
1. A mixture of triehlornaphtha-
lenesplusa trace of tetraehlor-
napthalene. Chlorine content
49.9 per cent.
2. A mixture of peuta and lie.xa-
chlormtphtlialenes. ('hloritie
content 112.(i |M*r cent.
A. A mixture of 90 per cent |>etita
.and hexaehlornapht haleaes
plus 10 per cent reliued chlorin- jj
.aled diphenyl. Chlorine con*
tent 03.0 per cent.
4. Chlorinated diphenyl. Chlorine
content 05.0 per cent.
The compounds were selected as reJ>*
rc'i uting a certain range in chlorina
tion 'ini .also because of t heir indust rial
imp*
'*. In each install'1* Ml ani
mal \po't*d, 10 rat - being placed
in e:
;Tliev were fed Purina
ih MI'yBog Chow supp f* fgs, DUlk and C(
iy*: V.This first 8rou
MfeeftW on July
^ gspoaure to numl ^Jornaphthaleni
sa- leth- The expo p impounds cea.* |risth- Co Ccto kC tire animals we I*-Bara frm group' fPfcflkd after 2 r
^ 15th, in order to
Conditions Main
Xrlehlorniphthali
Ulnchlornaph.
PtaU and hexacl
80% pent* and fene* plug 10% c
^Odorin&ted dip!
period would the affected v >iroup 3 wen yr exposure on gists' examinat ^..The avera ,A:.16 hours di r . Each mornir ased, and 4:00 p.m. t . sighed, etc C ..fotmity of ' shifted on
, * . r* o-j--
9042A&
WATER PCB-SD0000056627
th *> 7) V V*
effects of chlorinated hydrocarbons
2S9
Chow supplemented by lettuce, wax concentrations were somewhat
S milk and cod liver oil.
higher at the inflow end of the boxes.
fim*1 group of experiments was Preliminary runs showed that once
on July h 1936- and the last properly adjusted, wax concentrations
--posure to number 2 (penta and hexa- in the air remained very uniform from
*;:'|lomaphthalenes) was on November day to day, but to insure absolute
H pfa The exposure to the other three safety readings of temperature, air
Vgeopounds ceased upon November flow, etc. were made every night be
-' JSth* 0n October 15th reprcsenta- tween 10:00 and 12:00 p.in. as well
" . animals were taken out of expo- as on starting and stopping. At dif
./from groups 1, 2, and 4 and were ferent times during the course of the
*%ISW aftr 2 months on December experiment tests for free chloride were
v> mh, in order to see whether this clear made but were uniformly negative and
" TABLE I
CwomoNS Maintained in Inhalation Experiment from July 1 to November 10 and IS
CHLO RINE CONTENT
TEUP.
AV. CONCENTRATION or AIR IN BOX
TOTAL EX*
POSL'KC
AV.
DAILT EX
POSURE
{'THellomaphthalenea plus traces of Xs.fctmhlornaphthalene...................
% 49.9
&'-{*
lad hexachlornaphthalenes.... 62.6
c. mg./cm.
ran0<
m.
150-160 1.31 High 2 60 Low 0.10
160-170 1.16 High 2.19 Low 0 51
ko\lTt
1S90 1864
10 16
penta and hexachlornnphtha-
V!_ hoe* plus 10% chlorinated diphenyl. 03.0
105-175 1 37 High 3 17 Low 0 64
1890
1G
^^iaited diphenyl.
--------- --------------------
65.0 165-175 0.57 High 1.19 1S90 Low 0 23
1G
would bring about recovery in affected livers. Animals from iPWjp 3 were similarly removed from c^Pure on October 4th and killed
examination on December 4th.
average length of exposure was Yy ~Ur3 daily for G days a week, v-juorriirig at about 9:00 exposure
anc^ between this time and the rats were cleaned, fed,
' e^C`
or^cr t secure uni-
y f exposure the cages were
u a regular schedule, since
showed that under the temperatures used no decomjiosition occurred.
Table 1 shows the temperatures at which the various substances were held, the average concentrations per cubic meter of air, and the average; exposures from July 1 to November 1G and 18.
The concentration of chlorinated naph thalenes and chlorinated diphenyl in Ihc air of workrooms.--'fable 1 shows that animals have been exposed to varied concentrations of the substances under
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290 JOURNAL OF INDUSTRIAL HYGIENE AND TOXICOLOGY
t
tost. The concentrations employed in question is passed over heated may bo regarded as fairly representa num in an electrically heated quartt'-| tive of industrial experience. Prior to tube and the diluent gas scrubbed oA the initiation of inhalation experi a column of glass beads moistened wit^ ments a number of estimates of chlo sodium carbonate containing a trace( rinated hydrocarbons in the air of dif sodium sulfi.te. The beads are the ferent factories were made and the washed down and the chloride deter,^:
30CTI0N
Prefix
T Mfl. IN31CG DIAtl.
olid class beam
inn diam.
NOT ORAWN TO SCALE
3501.
r RESISTANCE FORKACE
SOFT(,I NOICHHMC/OfMtE) WICe
auAdrc.
7MM IKStDF D'AM-
6"PLATINUM*FIOSIL" ARAaC0K0IN/G"
IS.ZM < 3.81 je O.OOC54CM.
Fjc. 5. Dimensioned sketrh of combustion tube and absorption apparatus
concentrations chosen for inhalation experiments depended on these exami nations. The technic of analysis and the apparatus employed were the work of Frederick It. Millhiser and William F. Ilcmperly.
The method and apparatus used for determining concentrations of chlorin ated hydrocarbons in air were adapted from well-known procedures. The air
mined nephelomclrically as silver
chloride. Tebbcns (1937) lias recently de
scribed a method find apparatus which sliould be equally satisfactory for this ' work. In figure 5 we show a dimen sioned sketch of the combustion tube ^ and absorption apparatus as used by us in both our laboratory and field pa problems. The absorption tube is
t9, "
Kjmewhat
Tebbens's devices ar
In both sgtbmted h; *?icid and
sodium cc la our ca apt to be Jess than quentiy t actually f
" so small t
ether gre For this r use the m fa sensiti&s 0.1 mg
It k d should e: conrersio pound tc subsequei unless tbf low. An fa that tl any chic determin distingue gases but the resu! puted in
At the formatio: rinated i different
^stances repeated
the amo those US' must be
The c r&tua suit hi Willsc The. equ suction p\
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^^ksnewhat easier to wash down than is
i|'-'',ftbbens's but the essentials of the two are the same.
||\f|n both cases conversion of the chlo-
hydrocarbons to hydrochloric
l";*8C*d and subsequent absorption as carbonate should be complete.
F''-'|a our case concentrations in air are pv-#pt 1 ^ vefy lw--the objective is fflfea than 1 mgm. per cu. m. ConseItl^aently the amount of silver chloride wRfeetually formed in the final reaction is 'to small that it can not be determined !. either gravimetrically or by titration.
For this reason we have been forced to vV> Be the nephelometric procedure which
It sensitive to concentrations as low
esO.l mgm. per cu. m. of air. It is doubtful if the sampling rate
should exceed 1 liter per minute as emersion of the chlorinated com||>| pound to hydrochloric acid and its p*. fiibeequent absorption are not efficient r*_ unless the velocity of the gas stream is ^knr. Another precaution to be noted X fe that the method is not selective-- toy chlorinated substance will be ^determined. Furthermore it does not p distinguish between solid particles and
P*s but determines them all alike and results must, of course, be com
. jwted in terms of total chlorine/ r/ ' At the present time we possess in-
^rmation as to the amounts of chlo-
^ Ha*ted naphthalenes in the air of 30 [^different plants, and in a number of
?-e. Stances the measurements have been
t'fpeated several times. Frequently
*-vthe founts have been greater than ,,i* &ose used in our experiments, but it
f&*ust be remembered that the rats
RY.f-Ffat,a* combustion and absorption appa-
W-nl^et^ * fieN sampling is now made nillaon Products, Inc., Reading, Pa.
equipment includes flowmeter and 'n PUmp with a carrying case.
have been exposed for It) hours to art
atmosphere constantly impregnated
with the substance under tcs.t, whereas,
human exposure is usually a variable
quantity, intense for a short time and
then negligible. It is our opinion at
the present time that the concentra
tions of chlorinated hydrocarbons used
in our experiments would be dangerous
for workers in the case of compounds
above trichlornaphthalene in chlorina
tion. Fortunately it is easy to venti
late processes of manufacture which
require these substances and to reduce
air contamination practically to the
vanishing point. Such treatment of
the problem at once removes both the
possibility of systemic poisoning and
the annoyances that arise from cases
of ucnc.
.
Results of Inhalation Experiments.
1. Animals exposed to a mixture of trichlornaphthalenes plus small amounts of tctrachlornapthalcnc. Living animals were apparently en tirely normal. Autopsies performed near the end of exposure seemed to show slight swelling of the liver, and microscopic examination occasionally showed swollen and hypcrgramtlar liver cells. The changes were, however, never more than slight.
2. Animals ox()oscd to a mixture of penta and hexachlornaphthalenes. No abnormalities were, observed in the living animals. Rats were killed and uutopsied every li weeks. In the first animals sacrificed liver changes were observed. These were swelling of cells, slight granulation and hyalinization. In September and October these conditions were somewhat more ad vanced, and in November the process became stationary. There were highly
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292 JOURNAL OF INDUSTRIAL HYGIENE AND TOXICOLOGY
t9, :
granular cells, hyaline inclusions and mitotic figures, but no more than 2 months previously.
3. Animals exposed to a mixture of 90 per cent penta and hexaehlornaphthalencs plus 10 per cent refined chlorinated diphenyl. No abnormali ties were seen in the living animals. After G weeks the livers showed changes similar to those in the animals exposed to penta and hexachlornaphthalenes. These advanced in grade during August and September and then became stationary.
4. Animals exposed to chlorinated diphenyl. No abnormalities were seen in the living rats. After G weeks' ex posure there was slight liver damage which advanced during the next 2 months. The changes consisted in slight to moderate swelling of the liver cells, an increased granularity and many mitotic figures. Hyalinization was always present as a result of inhalation of chlorinated diphenyl.
Summary of the first inhalation ex periment.--In these experiments care ful observation of appearance, body weight, activity, blood, and urine showed no abnormalities of any sort. Yet after G weeks' exposure all the compounds with chlorination above trichlornaphthalene caused minor de grees of liver damage, and no changes whatsoever in other organs. There was no acute yellow atrophy or any thing suggesting it except that a slight degree of liver damage was always present and was quite clear in the liver sections examined microscopically. This damage had no detectable effect on the health of the animals. They held their weight, ate and behaved normally, being in every respect similar to the many people who have been
exposed to these compounds withou^lp illness of any sort.
The functional appraisal of the damage caused by certain chlorirud<d naphthalenes and by chlorinated phenyl.--There are no tests of fiver function useful in such minor degree*' of liver damage ns were produced in these experiments. Indeed the ani mals resisted the injury so perfectly as to display no abnormalities except upon histological examination of tl liver. The situation was perhaps similar to that met in industry, where," barring acne, the health of workers ia: these compounds has been good with the exception of the fact that in iso?: lated instances jaundice has occurred' which upon at least three occasions' has gone on to acute yellow atrophy.
During recent years this disease been seen following administration carbon tetrachloride, arsphenamina and cincophen. In the case of carbon tetrachloride it is known that a lot calcium diet and alcohol favor the p: duction of liver damage. For acute yellow atrophy that occasionally complicates use of the other two drug* no cause can be assigned. One ca: produce acute yellow atrophy with arsphenamine, but somehow or other; this now and then does happen to pa tients under antisyphilitic treatment
It occurred to us that something of the same sort might be involved in thi* problem. The human eases have been scattered and few. They have bcen^ isolated instances out of large groups of healthy employees who have had
equal degrees of exposure. It was our idea that perhaps many of these people
got liver changes such as existed in our rats, changes not recognizable through
any wC
Bjtion.
Rich cl ..disturb
fa
.' which f
fc-jt**. this re
i&alc
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pjy means other than autopsy examigation. Ifi upon the substratum of r- goeh changes, they got an acute liver ? ^rfurbance, acute catarrhal jaundice,'
very common disease but one HfeJjfch any of us may experience, would " && relatively innocuous disease go
jfftr to acute yellow atrophy?
ti Knowing that our inhalation rats j. M liver changes, but changes too ;V;-|Sght to cause recognizable symptoms, T " it decided to test their resistance to
Rjbstanccs known to cause liver de* Kruction. Carbon tetrachloride and
alcohol were selected. Having infor.. nation that 1.0 cc. of carbon tetra, chloride plus 1.0 cc. of ethyl alcohol
per kilogram would kill 14 per cent of normal white rats, we reduced the dose \ to 0.75 cc. carbon tetrachloride and ; 0.75 cc. of ethyl alcohol. ? ' This mixture was given by stomach hibe to the following groups of ani eals and with the results found in the following tabulation.
'sh Ssts fed 0.75 cc. per kgm. each of carbon tetrachloride and ethyl alcohol by
. stomach lube
frichlomaphthalene plus trace of telrapj^\t&l*r*aphihalene. Fed at 9:00 a.m., Nov.
" H, 1530. 10 rata. No deaths. . 1 Penta and hexachlornaphlhalencs.
5p;/ *t 1:30 a.m., Nov. 10, 1936. 10 rata. *** t .l died Nov. llth between 4:30
; 10:30 p.m. 1 died Nov. 12th at 3:20 p.m.
: ' 1 died Nov. 12th at 4:30 p.m. " l died Nov. 13th between 9:30
11:30 a.m. . I died Nov. 15th between night nf Nov.
14th and 12:30 p in. Nov. 15th. 2 died Nov. 16th between 10:15 p.m. ; Nov. 15th and 9:00 a.m. Nov. > 16th (stiff). --7 s0 Pr cent penta ntid hcrachtornaphS.iV and 10 per cent chlorinated diphenyl.
10:00 a.m., Nov. 10, 1936. 10 rats.
died N'ov. 10th 10:30 p.m.
died Nov. llth 10:30 p.m.
1 died Nov. llth between 4:30 p.m. 9:00 a.m. Nov. 12th.
2 died Nov. 12th about 1:00 a.m. 1 died Nov. 13th between 5:00
10:00 p.m. 4. Chlorinated diphenyl. Fed at 10:00 a.m., Nov. 10, 1936. 10 rats.
1 killed Nov. 10th at 10:30 p.m. (almost dead).
2 died Nov. llth between 4:30 and 10:30 p.m.
1 died Nov. 12th before 8:30 a.m. (stiff). 1 died Nov. 13th between 9:30 and
11:00 a.m. 1 died Nov. IGth between 10:15 p.m.
Nov. 15th and 9:00 a.m. Nov. 10th (stiff). Controls: Fed at 9:30 a.m., Nov. 12, 1936. 10 rats. 1 killed Nov. 13th for normal liver.
This tabulation summarizes into the facts that:
1. No normal rats were killed by carbon tetrachloride and ethyl alcohol.
2. No trichlornaphthalene exposed rats were killed, and this finding agrees with our inability to find lesions of moment in the livers of the animals that inhaled this substance.
3. The penta and hcxachlorinated
naphthalene, the mixture of these with 10 per cent chlorinated diphenyl, and finally the latter substance alone seem
to have produced conditions lowering the resistance to an agent capable of producing serious liver disease.
4. The sole lesion produced by this
tost of liver function was anile yellow
atrophy usually accompanied by jaundice.
This test of liver function was ac
complished with a substance which itself is an organic chloride and curi ously enough it is-the only substance
wc were able to find that was effective.
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In animals with the minor degree of liver injury which has been described we were unable to produce acute yellow atrophy or any variety of liver effect with arsphcnaminc, cincophen, butyl chloride, ethylene chloride and tetrachlorethylene, but carbon tetrachlo ride was uniformly effective in dis closing the existence of liver damage.
Recovery from, liver damage following removal from exposure.--Animals ex posed to trichlornaphthalenes plus traces of tetrachlornaphthalene being practically normal on removal from exposure need no consideration. In the case of the penta and hexachlor-
signs of liver injury will be mai) months in returning to normal. '
The effect of high concentrations (0 trichlornaphthalenes with traces of Utruf' chlornaphthalene.--The first group inhalation experiments showed t this material in concentrations ave; ing 1.31 mgm. per cu. m. of air rrjJ relatively innocuous, judged both by^ direct observation and by the carbon^ tetrachloride test. This is an in.^
teresting fact since such compound*!! cause acne, though less potently thaa^ substances of higher chlorination. In order to explore the matter further Aw oneof the inhalation boxes wasarranged ^
. fa other?
^ wcn
` ' one may tUornap toxic as
V. arc gpon th( 'irttions
The c:
' fic*la 1
' Jhcre cc ' gjcc done
bat in ' fey.; ported n
<ou!d t ' eotbing
TABLb 2
Conditions Maintained during Inhalation of [Item Concentrations or TlUCtt LORN A rimi ALEXES DLL'S TETIlACIILORNArilTIIALENE
MATERIAL
TEMP.
AV. CONCENTRATION OP Ain IN HOX
TOTAL AT. BULfXg EXPOSURE EXKMCtl&S
Trichlornaphthalenes plus traces of tetrachlornaphthalene
c. 137-200
mg./eu. m.
10.07
range
High 10.49 Low 5.78
kourt
1232
J
is m.ye*
naphthalene, rats after 2 months' re moval from exposure still showed swollen liver cells, increased granu larity, hyalinization and mitotic fig ures. The condition was not advanced as compared with rats killed at the time of removal from exposure but on the other hand 2 months were insuffi cient for recovery.
The same findings were true of the mixture of penta and liexacblorinated naphthalenes and chlorinated diphenyl and for chlorinated diphenyl alone.
Apparently the changes induced in the liver cells by these substances are exceedingly persistent and one must expect that an individual showing any
so that fumes from four glass contain-^ ers wore delivered to the air line instead of one. This resulted in the condition* shown in table 2. The animals sub
jected to these conditions showed no clinical effects of any sort. After I month the liver colls were sliglitly
swollen and over-granular and the wore occasional mitotic figures. These changes wore similar to the early effects of more highly chlorinated compounds, and progressed on!/ slightly during the third and fourth months. When rats in this condition wore given carbon tetrachloride and
alcohol, in some instances their live0 showed massive central necrosis and
#trophy Use of On Dec Ribjectc Bari zee tt&s ter; the ani and dee
904324
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EFFECTS OF CHLORINATED HYDROCARBON'S
fcfe cibcrs this did not develop. Fifty sSfiJL ^tre used in this experiment and D.:r may conelude that while tlie tri^-'gjomapbthalenes are in no degree as '^ZsJe as those of higher chlorination
not entirely fr.cc from cffms the liver if high enough conccn-
are inhaled over long periods.
P th& iaUoi%3
-M.
ft&fhe effects of high concentrations of " and hexachlornaphthalcnes.-- can be no doubt as to the dam-
jfat done the liver by these compounds fi^sst in the concentrations so far re-
^ ^JsHed no symptoms were caused that
fjfaStemM be recognized clinically and W-. &sthing approaching acute yellow
the liver after 35 days of freedom from inhalation. It is thus evident that penta and hexaehlornaphthahmes are markedly toxic compounds and that recovery from their effects is extremely slow.
The effects of penta and hexachlornaphthalencs, the mixture of these with 10 per cent chlorinated diphenyl, and of chlorinated diphenyl alone, when inhaled in low concentrations through an 8-hour day instead of a 16-hour day as in the first experiment.--Since steady human exposure to any of the compounds tested would invariably be for 8 hours rather than IG-hour periods, a further
gp>*v-
TABLE 3
a"ST. {Wjimnva Maintained durinq Inhalation of limn Concentuations of I'enta and TIIicE- X AC II LORN A1M1TH A I.ENES
LrT. QU9S\
M rmit
pm 50
'0:*'.
TEMP.
AV, CONCENTRATION AIR IN BOX
TOTAL
AV. OAILT
EXPOSURE EX POd CHE
ifVtU And hexachlornaphthalcnes..........
*C.
137-195
tug,feu. m.
8.S8
---------------- ----- ------------------------------------------------
range
High 14 .0 Low 5.75
Aourj
GOS
hour t
16
j^OsIrophy occurred except through the
<- bk of the carbon tetrachloride test. ^.0* December 1, 193G, 80 rats were
to the conditions sumjr/Bamed in table 3. This experment
terminated on January 21. All of *5^* ^iiuials lost weight and appetite
deaths began after 8 days of expo-
5' Fifty-five rats died, most of heavily jaundiced, 8 were killed
jp** microscopic examination, 9 were l^'Uled by the carbon tetrachloride test
.^tad 8 lived through the period of
/'^V5T>0SUre' ^''1C ''v<>rs
animals
ykv ^ fr examination showed marked
eg;;. degeneration, central in type
A; Xerosis of liver cells. Surviving .XJ^simala showed pronounced changes in
inhalation experiment was arranged under the conditions shown in table 4 which are quite comparable to those in table 1 except for the shorter inhala tion periods. Mighty rats were used for each of the three compounds tested. None at any time showed the slightest evidence of illness. Microscopic ex amination beginning after 0 weeks' exposure showed swollen liver cells, excess granulation, hyaline inclusions and occasional mitotic figures. These changes did not progress and were very similar to those in the animals exposed for 1G hours under the conditions set forth in table 1. The carbon tetra chloride test was uniformly fatal to them and one must conclude that eon-
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WATER PCB-SD0000056634
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JOURNAL OF INDUSTRIAL HYGIENE AND TOXICOLOGY
1S, no.
ccntrations of those compounds such as wore employed cause a certain de gree of liver damage even if inhaled for but 8 hours daily. This injury is resisted successfully by the rats just as was the 16-hour injury but it is none the less there and destroys the ability of the animal to resist the carbon tetrachloride test.
Summary of inhalation experiments. The findings that have been described briefly will be amplified upon the pathological side in a further paper by Dr. G. A. Bennett. What has been given is, however, sufficient to indi
men never inhale enough of these substances to get acute ye||o*gg atrophy. They may, however, acquit
a substratum of liver damage upoj'Hp which acute yellow atrophy may velop. Experience in a number ({f plants has shown how easy it "a reduce concentrations of these co pounds practically to the vanishing point, and every effort should be madj$ to attain such conditions.
carbons n
feeding ai " rate npP3
.*&rf for 1
{g>cntial r y:,i*thc id'
both n Indifferent
item to a
o far as ever way
Gross Feeding Experiments
The various compounds used wer^ ground as finely as possible and mbredj with a standard balanced ration fct&l
Trichlo Irtrachlori
iT.eo May until Nov
mng 3 gn
TABLE 4 Conditions Maintained during Inhalation of Low Concentrations of Three
Compounds DURING 8-IIoUR INSTEAD OF lC-IIoCR PERIODS
/ to the fc 5 end this c f througho
. UATXRIAL
TEUP.
AV. CONCENTRATION or Ata IN BOX
TOTAL EXPOSURE
IVwbnals ' which die
Penta and hexachlornaphthalenes..........
c. 149-193
mg./cu, m.
1.44
90% penta and hexachlornaphthalenes plus 10% chlorinated diphenyl............ 150-197 1.66
Chlorinated diphenyl.................................. 153-174 0.93
ran^e
High 2.58 Low 0.42
High 3.30 Low 0,56 High 3.23 Low 0.03
lours
920
912 920
kcxrt *.
loss of w wisting il i'death wa cpiratory
tion to tt. Istolc
(fight che of great si
cate that compounds more highly chlorinated than trichlornaphthalene are capable of causing liver injury when inhaled steadily in quite low concentrations. It is an extraordinary thing that even the most searching examination fails to show injury in any other region. It is not easy to grade the toxicity of the different compounds tested, but the chlorinated diphenyl is certainly capable of doing harm in very low concentrations and is probably the most dangerous. Industrial experi ence combined with these experiments make it appear probable that work-
the white rat. The food was pla<
in a single container, at which the animals in a cage had an equal chance, the amount of the compounds added
being reduced as the number of rati.< lessened during the feeding period^
The experiments were designed to git* an idea as to the possible toxicity cf g
the compounds selected and, if toxicity
was observed, some idea as to the site
or sites of damage.
.
The experiments were successful
both respects, and indeed one tnaj
anticipate that future appraisals of possible toxicity of chlorinated hydro*...^
_ Tdra t iff; Feeding
dosage of All the ar *1 were citl ..29,193G. ;4c;` At aut logically
effected. *mS. hyp-
sons ar there ncc *as a tre
Pen!a
Feeding dosage b
WATER PCB-SD0000056635
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kiaSocis may often be made by simple anj Jo not require the elabo-
apparatus and the expense neces, (or inhalation experiments. The SLtial reason for this opinion resides
identity of the lesions produced ^fcoth methods, and the fact that the Hjfcnt compounds so far studied
to arrange themselves identically as toxicity is concerned which-
Jgcts way they arc administered.
Krfrichlornaphthalcne plus traces of 'i&schkrnaphlhalene.--Feeding began
'.Sb'.May i, 1936 and continued
Hsatfl November 2,1936. In the begini:gm. of this mixture were added
j the food for 10 rats each day,
Wft-I this concentration was maintained
^fciffougbout the experiment. All the Pjgka&ls were killed except the last ^"sh'died on Nov. 2. There was no
of weight and no appearance of
. darting illness of any sort. The single &*th was due to some variety of reJ^fcilory infection which had no rela tion to the material inhaled.
^Htrtological examination showed lS$ht changes in the liver but nothing
(peat significance. is'Tdra and penlachlornaphthalcnes.-- JWing began on June 29, 1936. A
of 0.5 gm. daily was employed, toe animats sickened gradually and
either killed or died by August **, 1936.
T-At autopsy both grossly and histo-
y11/ the liver was the single organ "feted. The liver cells showed swell-
kypergranulation, hyaline inclu-
and vacuolation. Here and A*** nocrotic cells were found. There
f .s tremendous accumulation of fat.
an^ hcxachlorrmphthalcncs.-- 8 began May 4, 1936, a 3 gm. being used. By June 6, nine
rats had died. The last one was obvi ously ill and was killed for autopsy examination. Ail animals lost weight from the beginning and were ill. At autopsy-the liver alone, was affected, the lesions ohsorved being similar to those that have been described for tetra and pentachlornaphthalencs but worse.
00 per cent penta and hcxachlornaphthalcnes and 10 per cent chlorinated diphenyl.--Feeding began May 4, 1936 on a 3 gm. dosage. On May 16th feeding was stopped but all the animals went on to death, the last dying on June 8th. An autopsy the liver lesions were extremely severe and of the usual type.
On account of the high toxicity of the 3 gm. dosage, four rats were given a 0.5 gm. dose every other day. Feed ing began June 24, 1930 and the last animal was killed Sept. 11th. There were no deaths but all the animals lost weight. At autopsy the liver as usual was the single organ affected, the lesions being characteristic and ex tensive.
Chlorinated diphenyl.-- Feeding be gan May 4, 1936 on a 3 gm. dosage and was discontinued on May 10th. Seven of the 10 rats were dead by May 12th. The three remaining rats gained in weight but were sacrificed for autopsy purposes on July 8th. The liver changes began at once. There were no changes in other organs.
A second group of 10 rats was fed much smaller dose -0.5 gm. every other dayn Feeding began May 20, 1936. The first rat died on May 29th and four more before June. 21th. The remaining were sacrificed. Those rats that died showed losses in weight, while those sacrificed had recovered
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JOURNAL OF INDUSTRIAL IIYUIUXK AND TOXICOLOGY l,ScP<- Gt?.
their initial loss in weight and were
gaining. The liver lesions were similar
to those found in rats fed penta and
hexaehlornaphthalencs plus 10 per
cent chlorinated diphenyl but not so
marked.
`
Summary of gross feeding experi ments.--Of the various materials fed rats in large doses trichlornaphthalene plus traces of tetrachlornaphthalenc was quite innocuous. Tctra and pentachlornaphthalcnc showed definite liver damage. Penta and hexaehlornaphthalenes caused a similar grade of injury. The addition of chlorinated diphenyl to penta and hcxachlornaphthalencs increased the toxicity. Chlo rinated diphenyl alone produced liver lesions but in the dosage used was less effective than when mixed with highly chlorinated naphthalenes. In no case did the compounds used produce acute yellow atrophy but the lesions ob served indicate this might be possible if one found a dosage which could act for the proper period of time.
and rabbits,
dosage being raIcuJ-;XvL : gad on man
lated on the basis of 4 mgm. per eu. cmv:i2iX Afferent con1
of air. Again similar results wertMl "poems, it aI
obtained. In all such c-xperimenu^llf (Inly ca5l.!-v
there must of necessity be difTerencc*MI|
Oat the air
in tile degree of effect hut invariably^?
pore than 0
the liver was the sole organ affected^* # '. rf these co
and the lesions were those alread^ J} naphthalene
described many times.
'3 5$ g$snpound cr
Discussion-
These experiments leave no doubt as to the possibility of systemic effect*
jf-hgrt permir
Bony exam ptG jiints that ife&en greatlj
from the chlorinated naphthalenes an<P,,. chlorinated diphenyl. As in the ease^ of the effects upon the skin, the degree of chlorination seems to determine tbe^| systemic toxicity, and it is a striking thing that when trichlornaphthalene reached systemic effects arc never;
*> 'i. $) years, ai
. (id that
N been inexr baman exp1
Xtao and thinge thei ' fcqt today
marked and are. produced with th greatest difficulty. It is most remark-,4] able, too, that all the compounds'!
f . ff. Imp ... arrangemei
bydrocarbc
tested attack the liver and the livery
pr e sfeguard.
alone. During the past few months^
. kd tetrae
we have determined the organically^"
combined chloride in the livers of
Feeding Precise Doses by Stoinach Tube
The compounds employed were sus pended in gum acacia. In figuring the dosage the total amount a man of 50 kg. would inhale in an 8-hour day assuming an air concentration of 20 mgm. per ou. m. was first calculated and reduced to milligrams per kilo gram. The rats and rabbits received this dose each day. The compounds used were those employed in the gross feeding experiments and Hie results were essentially similar though the lesions were less severe.
mals very severely poisoned by pent*,
and hexaehlornaphthalencs but have|J
found no increase over normal figures, '
though the livers, as determined histov,,
logically, were very severely affected.^
At the present time we arc conducting^
inhalation experiments on a eldonaw;
ated diphenyl containing 55 per
of chlorine instead of G4 per cent in the case of the experiments reported^
in this paper and on a compound with^
a chlorine content between tri nndvi
I, ruehlornaphl hnlene. W'e
abo`*L
determining the degree to which th .
diet may increase or decrease toxicity,,;
Corrrois-vS professi
okm).
AS professi Ks de: $35 (19.
fixer. >T 85,118
-/>'lin<ANNp
' Arbeit' tel, 1.0
Subcutaneous Injections
this being suggested by similar
The same gum acacia suspensions upon carbon tetrachloride.
were injected subcutaneously into rats
In the basis of these experime
904328 WATER PCB-SD0000056637
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Y|j many field determinations of fjnt compounds in the air of work-
it appears safe and it is ceri?'^easily attained, to ventilate s6
ie air breathed does not contain ;J*'lban 0.5 mgm. per cu. m. of any i^these compounds above trichlor^gj^tJulcne. In the case of the latter ^gpound concentrations of 10.0 mgm. ' permissible. We know from
examinations in many different Lpajia that such concentrations have
' " greatly exceeded during the past years, and we are conscious of the
d-bti that our rat exposures have inexorably constant whereas
f^Wn exposure is never so ordered. and careful observation may
TtSaage these opinions as to standards, fei today we are convinced they are Impregnating tanks and other
&Uigements utilizing the chlorinated Ipirocarbons are easy to hood and to Ssfefuard. Compared with benzene, tetraethyl and many other com-
pounds, these substances are very little toxic and operations employing them can easily be safeguarded. It may be argued that where possible trichlornaphthalenc should be used, but this compound will cause acne and if employed very carelessly might do more. Furthermore, higher chlorina tion is often essential for highly prac tical reasons. The solution consists in thoroughly adequate ventilation plus good housekeeping around all wax containers.
A final word of caution bears upon the use of carbon tetrachloride as a wax solvent. Obviously this compound adds readily to the toxicity of the highly chlorinated waxes. If carbon tetrachloride is used, ventilation should be excellent, but in our opinion it would be better to dispense with car bon tetrachloride and depend on other solvents, especially upon those con taining no chlorine.
.N.,.
BIBLIOGRAPHY
^*toI3-Soffit: tude sur 1'intoxieation
t prolessionnelle par le trichloronaphAnn. de md. Rgale, 14, -122 Abstr. of paper by Tocraine, * A"VD MfirrfiTREL, B.: Dermatoses P^fessionnellos par la nnplitaline et
deriv6s. Prat. m6d. franc., 45, 135 (1934).
F- B., a.vd Jarvik. X. E.: Action of
?f^4'n chlorinated naphthalenes on the h v-FBrtr. proc. Soo Rxprr m,,| Mol.,
. u< 118 (1930).
K. B.: Kurzes I.ohrbuch tier -jn r. rhits- und Gcu erhehyaieiie. S. Ilir-
#>'; L'ipzig, 1919 (p. 251).
Mittelktadt, O.: GcwcrbcschadigunKcn
durrh Haftax (Trichlornaphlhalin). Inaug. dissert., Jena, 1935. Tebdens, B. D.: Portable combustion ap
paratus for field determinations of chlorinated hydrocarbons. Tills J.( 19, 204 (1937). Tei.eky, I,.: Die Pernakrankheit (f'hloraenc). Klin. Wehnsehr., 6, 897 (1927).
11Tociiaine, A.. Soi.e.n-te, MenA'iuki., .,
and Avanex: ('im|U.inti'-i|nal.re eas de dcrmalilcs par Iriehluroiiaphlnlinc. Bull. Hoe. dormnt. et sypli.. !/, 2115 (1934).
^SHSI
300
JOURNAL OF INDUSTRIAL IIYGIKNK AND TOXICOLOGY
fd. 15. w
Discussion
Dn. Cecil K. Drinker: We have had quite a long morning, but since Dr. von Octtingen has to leave, I am going to ask him to say a word.
Dr. W. F. von Oettinoen (Director* Haskell Laboratory of Industrial Toxicolgy, Wilmington, Delaware): I wish to con gratulate Dr. Drinker and his group on the very interesting and excellent work on the subject. I also wish to congratulate the Halowax Corporation on the fact that they didn't spare any effort to elucidate the prob lem so that the dangers which apparently are connected with the use of this material can be controlled.
I personally believe that there is no toxic material which cannot be used safely if it is handled properly. In order to handle such materials properly during the differen t oper ations it is absolutely essential to be famil iar with the toxicity and especially with the mechanism of the action. Since there is no animal which corresponds in all its physio logical characteristics to the human being it is important that such compounds be studied with different species of animals so that one can get a cross-sec tion of the poten tial dangers.
In addition, this fact illustrates the im portance of the pre-employment and peri odical examination of workers in such work. As was pointed out by Dr. Drinker, there are individuals who are apparently more susceptible to certain toxic agents than others. On the other hand, we have to try to detect the very first signs of incipient poisoning in order to prevent more serious damage. In .the present instance it is very difficult to find these very first aymptoms because there are no adequate methods, but I trust that in time the scientific profession will supply the medical profession with adequate methods which will allow the physician to determine incipient damage of the organ before serious clinical symptoms become manifest.
Thank you.
Afternoon Session
Dr. Cecil K. Drinker: In this discus sion I will call on one or two individuals ami I shall expect others to speak as their notes
incline them to. First of all I $\^\\ Dr. Sayers if he will open the discus for us.
Dr. R. It. Sayers (Chief, Division Industrial Hygiene, National Institute Health, U. S. Public Health Service, WutjU ington, D. C.}: Dr. Drinker, Ladies Gen tlemen: It gave me a great deal of plfu.^t| ure to have the opportunity to listen excellent and interesting discussion presentations made this morning. D,;
tD.h..rei.n.H.k.ea.rlo, waanxd IC- omrpigohrat taiodnd,, thhaevemedmisbceusrsseTd-So&f?
this matter with us, as well as the manel^), facturers of the diphenyls.
We have been doing some work but nol yv'f nearly as extensive as that carried on here.-''} The work that wc have been doing seem# to confirm the work that Dr. Drinker has riedon. I think there arc certain parts of 11 fj.: that we can very well keep in mind.
We arc dealing with toxic substances, batr. we arc dealing with toxic substances eaek b and every day in industry--harmful sub-'*stances, hazardous substances. That the^
can be controlled is well known, no matter vy what they are, and that we can use them and \ use them in a safe manner. Dr. Drinks^ has called your attention to the fact this apparently has been done and can b',i done in any of the plants where halowax il J
used. I have information from one or tw of the other men who arc in the audience^ that in plants where damage has been doolfj --skin damage and apparently liver damage^ to some of the workers--the manufacturer! Jhave since corrected the conditions and ap parently have adequate engineering coo-j trol supplemented with adequate medical
control. After all, the proof of the pudding i# ^
the eating. If the man does not get the diev^fr ease your engineering control is successful- NjJ If he does get the disease, no matter what you have done in the way of engineering, you haven't been successful. We must go hand in hand. Neither profession alona ^ ^ can he successful. Wc have got to wor^
together whether wc like it or not. I pen to like it.
There is one-other thing. A3 far as mate
rials are concerned I think we ought to b*
*lt too
't**#IuUy.
adapted f
jt. Anot
rkxix to t
yi* damn
^ppcoxinv
; *PPrc
srrer jus U might b
rare quit< happened
this ttectric c armor on gad was b proximate to s steel bottom of Impectim bide cap-!
lb fire ki loine. M
Here w Now we h doe to tt . induate t
Irfic'-l am info 6ot just t (Lmmabil thlorinati 'elao Lacri creases, a think that hire thes eoctrol tl re cam. . Perhap. are better present ti better. I rubmaruf roo-flamrr e{ their eh
Dr. C& you care t
Dr. Al of Occup Becticut 1 Conn;): I anything thia mate
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S&Ljrf enough to use every one of them sue u^ If this material is particularly
for a certain purpose we should use
irSL*Anther mate.rial that was used Pre_
i iM for insulation purposes, which ^*^"7fltmmable, caused a disaster in which
jgjlmately 167 men lost their lives. I
approximately 167 because they were
just sure whether it was 167 or 168.
fegflr^ht have been one or two more but they
P tt quite sure that 167 lost their lives. It
Weened when they had insulated a cable
" ' this material. They had an armored
cable. It was covered with lead
__ on the outside. It was 1200 feet long
isdtru being lowered into a mine shaft ap-
ppy.lm.tcly 3000 feet deep. It was lashed
'o' fei iteel rope. It slipped and fell to the
^bottom of theshaft. When the foreman was
to'tttptiDg it he set it on fire with his car-
tap-lamp. The carbon monoxide from
re killed those men that were in that
Many of course escaped.
_r/Htre we have one hazard, a fire hazard.
v|+ we have another one, a health hazard
to the toxic materials. We have to
_ ^iluate them. Certain of these materials,
informed, are also flammable. I am
Just sure how flammable they are but
mm^fifwnibility probably decreases as your f'fttfirfcu.tion increases. But your toxicity increases a3 your chlorination in-
according to Dr. Drinker, and I
that checks with other findings. We
these hazards to balance but we can
^Wltrol them. I feel quite confident that
Pwhapswccan find other substances that J^ir^k^ter even than this material. At the
^ am advised that we have no I am advised that in ships, such as
68' *3
important to have a
J*?^fraa61e substance for the insulation
their electrical wire.
,?
CecilK. Drinker: Dr. Gray, would
My** Ure to aay a word?
^_ Albert S. Grat (Director, Bureau
tj-r cuPa^onal Diseases, State of Condepartment of Health, Hartford,
` ^r- drinker, 1 don't think there is
r ^at I can say except that we used * 'naterial in Connecticut and we had a
number of so-called cases. All I can say is a confession of ignorance on our part at that time and I was very glad to see that your digging into the literature as thoroughly as you have hadn't elicited any further infor mation than we were able to get, basically. About all we could find was about the two cats that our friend, Lehmann, experi mented with. We got in touch with him and he confessed that the amount that he had given the cats and hi3 method of determin ing it were probably subject to very serious scientific criticism, and we agreed with him on that point.
We felt, and I am very glad that it is what you feel as a result of your experiments, that if we put in an efficient ventilation sys tem sufficient to prevent the dermatitis, we probably wouldn't have liver damage. That is what we did entirely empirically.
I think that is about all I have to say. I have been delighted to be here and to have as many members of my staff here ns 1 could jack out of the office. We have been de lighted to listen to the discussion.
Dr. . Cecil K. Drinker: May we. now make the discussion gene'ral and those who have questions please volunteer.
Mr. Manfred Bowditch (Director, Division of Occupational Hygiene, Massa chusetts Department of Labor and Indus tries, Boston, Mass.): I would like to second very strongly what Dr. Sayers ha3 said with regard to the approach to this problem in proper control rather than by prohibition, which seems to me wholly unnecessary not only in this case but in the case of other toxic substances with which we have to deal. The problem of proper ventilation seems to me relatively simple from what I have heard of the situation thus far. The problem of maintaining that ventilation properly does not seem to me quite so simple. I think it is going to be quite necessary that there should be a very adequate inspection of the plants using the materials and 1 ran assure you that that will be the case here in Massachusetts.
When this trouble first broke in this state a little over a year ago wc issued a quite Btrongly worded warning letter to all plants using these substances and it has all along
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JOURNAL OF INDUSTRIAL HYGIENE AND TOXICOLOGY
<PI. Itjjj
been my plan to follow that up with a fur ther letter bringing the situation as we now know it, as a result of Dr, Drinker's work, to the attention of users in this state. In that letter we shall unquestionably advo cate the concentrations that Dr. Drinker has suggested this morning.
One point that I think is worth comment ing on in that connection is the question of identification of the substances. It is ex tremely important from the state adminis trative point of view that employers using these substances should know what they are using. They are identified at present only by numbers. If we list those numbers in a warning letter which we send out there are likely to be changes in those numbers. The Halowax Corporation is a progressive con cern and it is going to be putting out bigger and better halowaxes all the time. The company's cooperation in this present inves tigation has been such that I feel assured that they will take the proper steps to see that we in the state offices and also the users of the products will know what we are using.
I wonder whether Mr. Brown would care to say anything about that.
Mr. Sandford Brown (President, Halowax Corporation, New York, N. Y.): There are some aspects of this situation on which I think I can enlighten the medical and state and civic authorities, with respect to the commercial and practical aspects. If you go into the research laboratories of any large chemical manufacturing company today you will find anything from one to a thousand different new chemical products which have not yet been put on the market. Some of those may or may not be toxic. The prob.lem so far as the chemical manu facturer is concerned is a question of timing. You have heard this excellent presentation given this morning by the Drinker brothers as to the work that they have done here. Should you take a product of which you have developed, say, 5 or 10 gm. amt spend $50,000 on research to determine whether or not it is toxic or should you wait until you havc determined whether you have a market for it?
If you are producing only one hundred substances a year you can sec that that would run into boxcar numbers in the wav
of dollars and rents before you PVcr . .
any. That is the. problem we have hack'd this ease. It has been on the market
25 years. Until within the past 4
there lias never been any intimation thatfe'
would cause nny systemic effects. tKq^J sands and thousands of workmen have di
with millions and millions of pounds of i tain of these materials, particularly the
chlomaphthalenes. Then we come to
higher stages, combined with chlorinate^
diphenyl and other products, and suddenly
this problem is presented to us.
1
We had asked various authorities fa terested in public health, going back oven
period of 15 to 20 years, to investigate
but there wasn't much enthusiasm for Mr. Bowditeh suggested that we take it |
with the Drinker brothers at this inatlti'
tion, which we did. You know the results
of that work.
Now so far as these changes are cos-v eerned, they are beyond our control to 4*
certain extent. We will manufacture &.
product--let's call it 1251. It has certain
chemical and physical characteristics,
is supplied to a cable manufacturer. It li
composed of certain constituents. T!
may be some tetrachlornnphthalene,
chlornaphtiialene, paraffin, a little pitci
or bitumen, and possibly some chlorinated
diphenyl. It does a certain job but-
wants it to a little more plastic or he wants
its viscosity or the specific gravity changed;
Possibly by a change in those constituents
of only 1 per cent we can get that particular
property. We can't sell it to him as
same product so we put a new number
U*?Basically, however, if the variation in
chlorinated naphthalene or the clilorina
diphenyl constituent hasn't changed,
toxic property of that will not change. When it comes to a question of cooperat*.
ing with the stnto authorities in that con
nection, if there were some major chanfi made in a product we would have no be**tnney in advising them and we would *1*
advise our customers. Virtually every coo ;
sumer of these materials at sonic time of _
another has been given their technics* )
chemical designation along with their vari ous properties, whether they he physics Of
chemical.
,
Those arc some of the practical prob wn* >
IS
90433k WATER PCB-SD0000056641
Hi'i&L if. `1 EFFECTS OF CHLORINATED HYDROCARBON'S
303
wtich all manufacturers of chemicals &&?'*!*** today, particularly in the
. jjjjjjc organic field where the devclopjj 80 rapid that our sales departments
^< 2?tiven keep up with the research departClv --t.sometimes, in knowing what they are
jf&laf.
F. R. ICaimer (Assistant to Man-
.VaWf York Wireworks, General Electric Co., m? Ywk, Pa-): I am certainly pleased to have iPf'iiida opportunity to say a few- words with
to the experience we have had at York plant. I perhaps should say that
In this case experience alone has been best teacher. I have lived with the {/'pprobltm at York with the men who went JpVcXttWgb the experience from its beginning. rL-'-.Tit l* only H years ago that we had in the >;Bdfhborhood of 50 to 60 men afflicted with SViwrfouj degrees of this acne about which you V:fl know. Eight or ten of them were very j-N'srttrtly afflicted--horrible specimens as far I their skin condition was concerned. One Aadifd and the diagnosis may have attrib-
his death to exposure to halowax |i'^npors but we are not sure of that. There r'c.'/imao atrophied condition found as a result
the autopsy but we are not definitely sure .a'v&it it was or was not connected with his
Knowing the man as I did when he l employed, with the superficial examina-
that he had, he appeared to me very pallid in his appearance, and I would _wy from my poor knowledge of the cal make-up of the human being that pwsented a healthy appearance. HowJ'j^fiftwasonly for a6 months' period from
time of his employment that he com-1 ^.flaked of this constipated condition and we
sa^Brraed that he see his home physician. It **t^dly developed to the point where he was c the hospital and in a very short time he
If*-
Sh-*ore Berious than that perhaps is the fact
' ka<l 50 other men in very bad condi,, M far as the acne was concerned. The
* ttacfln that several of our executives
^row" ** out--get it out of our ! They didn't want anything like `'IsU If3* *reaHnB w`re. But that was easily
S"-( J>t not so easily done. We might just have thrown our business to the four and said, "We'll close up," because
there was no substitute and there is none today in spite of all the efforts we have made through our own research laboratories to find one.
But we diil develop --and I was most closely associated with it--and set up a routine for bringing these men back to nor mal health conditions. A number of them were sent to Dr. John H. Stokes and to Dr. O. H. Perry Pepper of the University of Pennsylvania Hospital, and the others to Dr. Isaac R. Pels at Johns Hopkins. Through their recommendations and studies we employed a trained nurse and two local physicians and you might say established a smnll hospital and its facilities at the plant. Through the application of quartz light, x-ray, mechanical removal of comedones and the treatment of pustules that de veloped in later stages, an utterly strict routine where the worst cases were adminis tered to each day for a period of 15 to 20 minutes, another group who were less seri ous three times a week, and still another group once a week, we have in this year and a half brought each and every man back to a normal skin condition. Those who were very seriously afflicted do show scars, but otherwise their skin is as healthy in appear ance as my own. I tell you we are very proud of the fact that they are still all em ployed and the amount of halowax that we are using today is even greater in quantity and in types than we were using a year and a half ago.
With the adequate ventilation system we have installed, with the routine for change of clothing from street clothing to work clothing when they come to work and the roverse of that process, with the assurance that a shower will be taken before the street clothing is again put on, we have found no recurrence of this skin trouble. Each and every man working with halowax products, either from solution, from solid compounds or handling the wire insulated and treated with it, is examined twice yearly with a com plete physical examination, including blood analysis and efforts to determine any liver damage.
However, there is the point which was very definitely brought out this morning. We do not know as yet when this thing starts. I believe it would be of great help
If 1, /
JOURNAL OF INDUSTRIAL HYGIENE AND TOXICOLOGY
mj'M
to us all in industry if some very funda mental work was done on humans, as Dr. Jones mentioned before we came into this meeting, some control in fundamental work to determine some method whereby we may determine the inception of any liver dis order.
We have had our men examined in groups three times since the trouble developed and nothing has shown up in any one man. We have learned and appreciate the fact that we must handle hazardous materials, but we have learned how to handle them. It has been a very great experience for us and for myself, and again the best teacher.
Dr. Cecil Iv. Drinker: Can you recol lect the air concentration that you are main taining now with your present ventilating equipment?
Mr. F. R. Ivaimer: We have had two examinations made of the air by Mr. Wil liam F. Hemperly and they average from 0.2 to 0.6 mgm. per cu. m. We recently dis covered one condition which was found as the cause of a high reading in one of the examinations. The compound is one that is not manufactured by the Halowax Cor poration that is used rather infrequently, perhaps not more than 50 gallons of it in a 6 month period. It is in the form of a paste, reduced with solvent to a paste form, and it was not known that it contained a chlorin ated solvent in certain percentage. We dis covered it only recently through the analy sis of a sample and we found that that was the cause of throwing the results off to a high value. It was then about 8 mgm. per cu. m., I believe." That is going to be eliminated now. That is a combination of toluene and carbon tetrachloride solvent. When that compound is exposed to the air the chlorin ated solvent odor is completely masked by the toluene. It is lost. I was nble to detect it only by removing the head of the drum and immediately smelling the odor of carbon tetrachloride. As soon ns that head wa3 removed for a period of 10 seconds the tolu ene predominated and we had no knowledge of the other being in there.
Mn, Arthur G. Lever (Research Engi neer, United American Bosch Corporation,
Springfield, Mass.): Do I understand yQ4
to say that those men who were afflict^
arc back on the same job?
'
v?
Mr. F. R. Kaimer: They all returned U.'
normal skin health, as I say, and are work,-?
ing on the same job.
Dr. Cecil K. Drinker: Dr. Schwart^
you have seen a good deal of this general;
subject.
Dr. Locis Schwartz (Medical Directed Dermatoses Investigations, United Stat Public Health Service, New York, N. Y.)J I am primarily interested in dermatitis sod it was only because of my researches in that field that I happened to come across infor.$ motion given to me by Dr. Gray that then
were some cases of yellow atrophy of t`h"V( S
liver attributed to halowax. I ran on! talk from personal experience about theskia cases. I know from what I have seen and; from what I have heard from doctors wh*|
have been treating these cases that if they-? are treated like an ordinary acne vulgirisJ and kept away from further large expoaura they all get well, with the same results si acne vulgaris. Those who have large pns* tulos may have scars resulting and who have superficial pustules or only ci dones won't have any scars.
As far as prevention goes, I felt even b9*|fore this investigation was undertaken that this substance, like any other poisonooi substance, can be handled and used in in* dustry provided proper safety precautiooi are taken, and I bo advocated at the meetin| in Pennsylvania when this was discussed,'
About ventilation and safety precao* tions, I think that while we cannot, with o present knowledge, detect by any chemical,*,,
tests the early symptoms of intoxicatic* from this substance, the skin offers an easy ^ way of proving whether your method ventilation is efficient or not. If there art any cases of acne ur of this dermatitis occur* ring in a plant where halowax or the chlorta* ated naphthalene or chlorinated dipbenjr arc used, then that shows that there is fie ten t concentration of these substances U ,f the air to cause plugging of the follicles an _jji
to cause a skin condition. If there is sum* cient concentration to do that there may
reU m.
904334 WATER PCB-SD0000056643
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EFFECTS OF CHLORINATED HYDROCARBONS
;.__cient concentration to cause systemic
Mr. Warren A. C'ook: I am not quite
booing in the fe>v people who are hyper- sure that I have in mind exactly what you
!t2tive to the action of these hydrocar- want in that regard. In connection with Jc Everybody is not hypersensitive to sampling?
V~Y k they were, of the thousands of 2jle who have been handling these sub-
Dr. Cecil K. Drinker: Yes, In con
ft&aeeSi more would have contracted this *nd it would have been reported fitj much earlier. This material was used
nection with the whole technic of determin ing the material in air, length of sampling, type of apparatus, and so forth. It has
|i Germany as early as 1914 or 1915.
been suggested that we endeavor to agree
' While I cannot add anything to the upon some uniform procedure for that and
ptthods outlined here for safety in the way as figures begin to come in, as they will in
ventilation and so forth, I can say that the course of the next couple of years, we
8you 8 into a plant and find that there i3 will at least have them on a comparable
lay acne present among the workers with basis.
&{g material you will know that there is
HsSelent of the substance in the air to cause
Mr. Warren A. Cook: In that regard
se and consequently sufficient perhaps to there is no question but what the determina
dangerous to the few people who are tions and results of analyses of the concen
lyperaensitive to its action.
tration of injurious materials in air, corre
,, Da. Cecil K. Drinker: There is a prac lated with pathological findings or freedom
tical point in regard to the question of deter- from pathological findings, are real factors
jisining these substances in air. My brother in further substantiating toxic limits which
pointed out this morning that there are are originally given us from animal experi
trreral pieces of apparatus for doing this. mentation. In order to obtain data which
U has seemed desirable to a number of the are of value along that line it is desirable to
BKM who are here that during the next eou- know to what extent, in terms of milligrams
pto of years, while we are in a position of per cubic meter, workers are exposed to
taming, that we endeavor, if we can, to in breathing any potentially injurious
(online our analyses to one piece of appa- material.
bo that at least our results will be as
It seems to me that one of the things that
fccspar&ble as we can make them from place should be done, which many of the plants
to place.
and many of the organizations equipped to
S3 r I don't know much about this phase of make determinations of injurious materials subject: perhaps, Mr. Cook, you have in air should do, is to mnke an effort to
** We**or two about that.
develop one group and series of results
which will represent average exposures of
y,V Warren A. Cook (Chief Industrial workers to chlorinated naphthalenes. In Hygienist, Bureau of Occupational Dis- getting that figure I think that it is of great
A'?*** tate of Connecticut Department of ` importance that we should consider average
Hartford, Conn.). On the deter^loation of the halowax I wonder if it ^ Wouldn't be preferable to have Mr. Hem-
discuss the method he has been using T^u8bout the country for the determinaBon of chlorinated naphthalenes.
daily exposure. There is a tendency very often in taking samples of air to determine maximum exposures, to get the exposure over a 15 or 20 minute period when the worker may he actually tending a pot where the material is being used, whereas during
the subsequent half hour he may be 40 or f Cecil K. Drinker: I think so far 60 feet away from that particular location.
v *8 concerned it is best to leave that Therefore, for one thing, it seems to me it
1 1 <^1CU89*na
Mr. Hcmperly and Dr. would be extremely desirable to obtain in
%5.Tafterward. But the question of SJ Ruining some uniformity of technic for
*. least is, I think, a matter of gen " ^ unrest to ua.
formation in as ninny plants and as many locations ns possible of the average expo sure, taking into consideration not only the worker's maximum exposure while actually
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JO CRN" AL OF INDUSTRIAL HYGIENE AND TOXICOLOGY (Sept. /9J7 '
at work with these materials but also his hefore the A. P. H. A. in October as one of
much smaller exposure anil possibly even the projects which we shall carry out attij lack of exposure as he may go to other parts that time.
of the room or even to other departments
As I have not given this consideration, I
during the course of the day.
am afraid my discussion is not as connected
Another type of determination which ' as I might wish it to be. We have a r
Beems to be extremely desirable to have is problem here and one that deserves Botna'c
concentrations of the chlorinated naph study.
thalenes at certain reference points. I
believe that Mr. Hemperly very carefully
Dn. Cecil I\. Drinker: Would it be of"
duplicated these reference points in each service to the American Public Health Asto-!
of the plants where he took his determina ciation Committee if a sub-committee from1
tions. He took the samples, I believe, at this meeting, collected perhaps by my;
breathing level and a certain measured dis-' brother and those of you involved with the**
tance from the pots where the chlorinated problems, were to make a recommendation^
naphthalenes were being handled, so that to the A. P. H. A. as to the things you haril
next year he could go back to those same brought up and as to suitable apparatus,-.,
locations or others could take determina and let the final statement come from the'
tions at those same locations, which are Association after they have considered that;
definitely fixed and recorded, and learn material?
whether, due perhaps to clogged pipe lines
or to fans which might become loaded with
Mr. Warren A. Cook: I think that]
the condensed chlorinated naphthalene, would be a splendid idea because we hart?
there might be poorer ventilation than origi a bulk of information on this particular
nally designed and higher concentrations material. A number of individuals hart'
of the chlorinated naphthalene than origi given much thought to the development of i
nally determined.
apparatus, both the combustion method^
It seems to me that it would be an ex which we have here and also the coQtiauo
tremely desirable thing to have made avail record type of apparatus which Profe
able for all of us who are making these Drinker mentioned this morning. I th
determinations these reference points so that it is a sufficiently important project :
that in Massachusetts and in Connecticut, that a sub-committee made up from this 1
at one plant or at another, a considerable group could give that committee a very4
group of workers could be taking samples at definite steer.
_
this one particular point with reference to
(Personnel of the Sub-committee: W. A-'i
the source of generation of the vapor. Such Cook, chairman, A. L. Coleman, H. D. El*;
results would permit a comparison of knowl kins, W. H. Fulton, S. W. Gurney, E. R-|
edge between plants.
Ifayhurst, W. F. Hemperly, F. W. Sehl, and ,
In that regard it happens that there is a A. N. Sctterlind.]
committee of the American Public Health
Association which is charged with the dcvel-
Mr. Hervet B. Elkins (Chemist,
opment of chemical methods for determina sion of Occupational Hygiene, Massacho*^
tion of atmospheric contamination such as setts State Department of Labor and that now under consideration. It seems to tries, Boston, Mass.): In connection with(
me that it might he a very desirable project what Dr. Schwarts has said, I am notsurs-'j for that committee to consult with the in that I am in complete agreement as regard*^
vestigator of the Ualowax Corporation and the use of skin lesions as-warning agenU-
suggest to all of those who are doing work It is my understanding that in insulated^
of this type, after some discussion, what wire plants the chlorinated diphenyls at*j reference points could be adopted and also very commonly compounded with the chlo*.^
what should he done in connection w itil get rinated naphthalenes. It is also my undef;j
ting these average exposures. Asa matter standing that these are more likely tocau**j
of fact our committee will discuss that very a severe skin irritation than the straip v
feature and possibly include it in our report chlorinated naphthalenes. On the ot
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WATER PCB-SD0000056645
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effects of chlorinated hydrocarbons
307
sv^.iv .
^{iasJ.
fthramt
tih?er-
Drinker's work one straight chlorinated
would naph-
to attempt to get the concentrations low. We saw this morning that the effect of these
wU nearly as toxic at least as the products was on the liver and that if some
L^AfrMttre of it with a small amount of chlo- one working in these products developed
tfa*ttd diphenyl.
liver damage from some other source the
--`-V.yTjg iJjg condenser factory where we had chances of his having serious trouble was
r eases there is no chlorinated diphenyl increased. Therefore, inasmuch os there is
S^J and no acne of the type described in no test to tell whether a person has had liver
^ reports on the insulated wire factories, disease, certainly in the preliminary medical
r- ifFv:'
examination of applicants for work the his
igt. T DS.R. Emmett Kelly (Monsanto Chem- tory at least should be gone into very care
St. Louis, Mo.): I can't contribute fully for a history of previous liver diseases.
gsfthing to the laboratory studies but there
There ore other things that should be
^lytecn quite a little human experimenta- taken into consideration also. One is the
the last several years, especially at history of syphilis, because syphilis does
" pltnts where we have been manufactur- have an effect on the liver. If there is any
frj this chlorinated diphenyl. It has been history of syphilis I don't think that that
"" robservation that although on one occa- man should be hired. A Kahn test should
t&a we did have a more or less extensive be taken and I think that it would be a good
fef'4 rlf* f akin eruptions which we were never plan to take Kahn tests on men at stated
S-Lv.iH* to attribute as to cause, whether it was intervals, because they might develop
US Safarity in the benzene we were using or to syphilis after they are hired.
ft* chlorinated diphenyl, we have never had
I think those things should be done even
Sty systemic reactions at all in our men. though we feel that if the concentration of
P-J?- W hare examined them very closely both these vapors in the air is kept as low as was
&em what laboratory tests we thought recommended this morning, the chances of
sight help us and from the clinical view- having toxic effects are very small.
Also from chlorinated diphenyl
i there have been no cases of systemic
Mr. F. R. Kaimer: I would like to clarify
Qg reported.
a point of Dr. Hookey's.
I don't believe that we can transpose the
You mentioned at the beginning of your
laboratory results into the actual humans talk that your experience in acne condition
if-. without paying considerable attention to was more pronounced from the compounds
volatility of different substances and the of various materials with chloronaphthalenc
they are being used.
j* '
jsJDs, John A. Hookey (Consulting Dcr-
than with the straight chloronaphthalcncs. Did you mean by that, that the acne condi tion actually was more pronounced with the
Halowax Corporation, D.etroit, compounds than with the straight clilorn-
.r~M: i have had considerable experience naphthalcnc or was that due to the fact that
v %
the dermatological angle of this prob- you were in a plant operated in a different experience at the Halowax plantfashion? In other words, you handled your definitely was that the derma- numerous wire compounds in more of a
^,wsoi did increase when compounds were batch operation. That is my understand
hu-***! rather than the straight chlorinated ing from Mr. Brown.
jfigPhthalencs. jJ'rxini the discussion we have heard today
Is it a fact that the straight chloronaph thalcncs are less harmful in so far ns acne
^ ^3ervatin Dr. Drinker made is concerned or is it because of the handling
^ chances are that dermatological of batch compounds?
emS " disappear along with the other
true. However, I think that
#rwT*11 i)recau*,'onsi certain insurance rneas^_yU niight say, should be taken in
Dn. John A. Hookey: That is a question that would be difficult to answer. I based my statement on the fact that in taking a
men who are going to work with general survey ol these cases after I started Prducta, even though we are going working with them the men in the plant said
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WATER PCB-SD0000056646
JOL'UXAL OF INDUSTRIAL HYOIKNF. AND TOXICOLOGY [SePpti.. tttfj
that they developed acne more often and more severely after they started making compounds. It may he that it was in the method of the handling.
Mr. F. It. Kaimer: You say that the con dition increases with the increased chlorine content and wc are attributing the acne pri marily to the chlorine radical. If that is true, what are we to associate insofar as these various other constituents arc. con cerned, surh as various plasticizing agents? IIow much do we know about those insofar as development of acne is concerned? Some of these compounds have a half dozen con stituents in them other than chlorodiphenyl and chloronaphthalene. We are at the present time considering the chloronaph thalene as the basic element responsible for the acne condition which we have. We know very little about what the other mate rials may or may not do.
Dr. John A. Hookev: I don't know about these other materials. Perhaps Dr. Schwartz would know something more about them.
Dr. Louis Schwartz: It is well known in industry that there arc many compounds that cause acne. For instance, paraffin acnes and oil acnes have been known for a long time. Paraffin acnes, wax acnes, are simply a mechanical plugging of the fol licles of the skin by the minute particles of wax that fall on the skin. 1 think that the acne caused by these chlorinated naph thalenes and diphenyls, because it is caused by both--I was down at the Swan Chemical Company where they make chlorinated di phenyls and they have acne there just the same as over at Wyandotte where they make the chlorinated naphthalenes--I believe that that is caused by the same thing, a blocking up of the follicles of the skin, the formation of the comcdone and then the comcdonc becomes infected and forms a pustule, They don't all pustulate because they don't all become infected. Many of these men never have any pustules. They just have little white elevations on their skin.
In those people who are in the acne age, the youngsters of 18, 20, 22 and 23, acne
vulgaris is moat apt to occur. The s: eb^
ou.s glands are most active and they seem
have it much more than the older people
whom the sebaceous glands are not *
active.
Wc keep a clipping of all articles relatia^
to industrial dermatitis in my office and]
recently read an article in a German i
zine in which they report in Germany!
similar acne condition from chlorinated
phenols and chlorinated benzenes and i
waxes. It seems that this ac.nc-like cond
tion is not peculiar to halowax or chlorh
ated naphthalenes or diphenyls hut
occur with any condition that blocks uptbjj
sebaceous follicles of the skin.
~
Dr. Rotal Meeker (Special Agetrt,* State of Connecticut Department of Labor,^ Hartford, Conn.): I am full of question*.!
As a statistician I am a little bit suspicions' of averages, so I should think that we should] take maxima as well as averages in getting j at the threshold dose or the dangerous l*3 pregnation of the atmosphere with then! poisonous compounds. I just wanted to| drop that os a hint for this committee to consider in its work.
In spite ol what you said at luncheon,^ Dr. Drinker, I still think it is rather impor- j tant to determine how the plugging of tbs? pores actually does occur, whether they uw ' plugged as Dr. Schwartz has suggested,'!
from the particles falling on the outside ol ' the skin or whether they are plugged, as many doctors have informed me, from insid# as it were. The fumes are breathed, U*>! substance gets into the blood stream. It l ; thrown off through the pores of the skin aod^j the pores are plugged. I think it is rathtf^ important to determine that because ttj seems to me, from the slight knowledge thsij
I have of the industrial application of 1 wax compounds in insulating wires, the plugging of the skin, if it is just an i side plugging, may take place cither handling a solid substance or from the.
coating on the wire after it becomes c I haven't heard anybody say anytl
about those Massachusetts cases of ' severe dermatitis and I am not so Bure ba i
what there was some question of liver dam
age there. Nobody has said anythingabou
them at all. There is no question tbert
tfct th<
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904338 WATER PCB-SD0000056647
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-i EFFECTS OF CHLORINATED HYDROCARBONS
tf.pL tt"0' *'
309
%:<
Tv.ru-ihe condition, whatever the- complica- wax we had a head start as far as the
jnight have been, came from handling ventilating system was concerned, since
wire, in a confined area of course. ours was already installed and adaptable to
rf7lhink this necds a grcat deal morC study' a compound with a benzene solvent rather
'Drinker, than you and your associates than a melted halowax compound. In order S?ikw been able to give it as yet. AH I am to keep the fumes of a highly volatile sol
about is the way we can administer vent under control we did develop a prac
"y-j. omicctive labor laws in order to protect tically complete enclosure for the container
' *Mk the employer and the employee. ^IjUrtened with very great interest to the
Impositions of suggested pots for the appli-
in which the compound was placed and exhausted that container in order to prevent any escape of the fumes from it. When we
of halowax, chlorinated naphthalene changed to the halowax compounds we fol
diphenyl. It seemed, to me that they lowed the same scheme of applying the
$JjfVtery much to be desired. I don't see compounds and used a completely enclosed
the application of the halowax com- pot. There is a hole in one side for the wire
if it is necessary, as I assume it is, to go in and one on the other side for the jftMiW this rather dangerous substance, can't wire to come out. There is enough exhaust
CvV&sdone in a practically closed pot. If you suction on the enclosure to prevent any
Dr. Drinker, I wish you would ask fumes from getting out of the openings
m*r. Reeves of the Rockbestos Products where the wire enters and leaves. Of course
L-Owporation to tell how they have handled periodically it is necessary to open the pot
' 8. U I am any judge of equipment and to replenish the compound or make adjust
devices they have come as near to ments. In that case we have the ventilat
Vt/:Jiinting entirely from the atmosphere ing system interlocked with the door that
*:'.<p8 contamination from fumigated or evapo- the operator opens so that when he opens
ptitd halowax as anyone. All of the appli- it he increases the amount of air travel
v*~ iloc of halowax, either in the melting pot3 about ten-fold.
here it is applied to the wire, is done
'^"Eadtr hooding and with ventilating appa
Dr. Royal Meeker: What is the veloc
ratus, and it seems to be entirely adequate.
fxik
Mi. B. H. Reeves (Vice-president and
vjtXOtteta! Manager, Rockbestos Products
ity when the door is open?
Mr. B. H. Reeves: With the door wide open, at breathing level the velocity is 2UO
q^Cwpor&tion, New Haven, Conn.): 1 will be feet. That is the linear velocity. Wc
riad to tell of our experience if it will check that every week on every opening at
the picture along. Our experience has Iwamore or less parallel with Mr. Kaimer's
jhaamuch M we manufacture the same type
every machine with a velometc.r, a small instrument which is easy enough to operate and reads directly. Whenever the velocity
wire. We have avoided the serious pic- falls below that figure the pipe connecting
>thal he ran into, probably due to the that machine is taken down and cleaned,
- that shortly after 1923 we were using because there will be condensation inside
M a8lvent for asphaltic materials. the pipe to cut down the air (low anil reduce
[ , 1 K1 into anemia difficulties with ben- the ventilation efficiency. fumes and had to install a complete
Waling system to remove all those from the machines that applied the
Dn. Royal Meeker: What do you think of that trap device shown?
- ?cunds to the wire. Following the illation of that equipment we were able
ft * substitute for benzene, so we got it of the picture.
Mr. B. H. Reeves: I don't know what to think of that. I don't know whether it would be practical or not. I was going to
, &rc
in the same fix as every one
1 a far ns finding a substitute for lialu-
" There is none that wc know of. Con-
^lly when we went to the use of halo
ask Dr. Drinker whether in passing the air laden with halowax fumes through the boxes of rats there was any deposit of halowax in the enclosure.
JOURNAL OF INDUSTRIAL HYGIENE AND TOXICOLOGY I.S.- PL
Du. Cecil IC. Drinker: Yes. It is detectable readily through the outflow pipe.
Mr. B. H. Reeves: Those in the far end probably didn't get the concentration.
Dr. Cecil K. Diunkeu: We change the position of tlie boxes each day. The ones furthest away move into the nearest posi tion, so tiiat over a period of weeks all are exposed equally.
complaints were bona fide. We h:t<| no<
Acuity in handling cold wire and the i
had no skin trouble. Yet when they the same thing with possibly the application^
of heat in tunnels, ships and so forth, tb
.actually did develop trouble.
.
We have used, of course, the icterus itukj*
in following some carbon tetrachloride ca*to and I wondered what you have to say abo^;! that. Is that of no value at all in the ctirf
of liver damage in this material?
*
Du. Emery R. Hayhurst (Consultant in Industrial Hygiene, State Department of Health, Columbus, Ohio): I would like to ask if it wouldn't be possible to put a cold water line around that trap and deposit it all before the air escapes from the trap.
Mr. B. H. Reeves: We have tried cool ing the surface of the exhaust pipes in order to concentrate the deposit in one place and make it unnecessary to remove long lengths of the ventilating system. While we have found a slight advantage in doing so it hasn't at all paid for the expense. It is much easier to take the piping down. Con sequently I doubt the possibility of remov ing it all by cooling the surfaces of the trap. It might bo possible, by building a labyrinth of refrigerating coils, to collect it. But then you would have the problem of remov ing it from the coils after you lmd collected it and it would involve rather complicated procedure.
Dr. B. L. Vosborch (Medical Director, General Electric Company, Schenectady, New York): We have heard about the pos sibility of preventing liver damage and skin trouble among manufacturers of wires and cables and so forth, but like the old rhyme, every dog lias fleas and the fleas have fleas, wo also have customers who use wires and cables in tunnels, in enclosed spaces, splic ing them together and doing all sort3 of things. I am not at all certain that wc know what the concentration of these chlorinated hydrocarbons is under those conditions.
About the time we were having so much trouble at our York factory some of our customers began complaining. We thought we were having a hysteria of lialowax mania throughout the country. Some of their
Dr. Cecil K. Drinker: I don't think ja* until it gets so extreme that we know itujJ*
way.
Dr. B. L. Vo.sdurgii: I did write downt^ few questions that came to mind. Someefj! them have been answered and some argg foolish but I shall ask them anyhow.
It occurred to me that if trichlornap^ thalcne has been proved to he praeticiIljJ innocuous, isn't it a problem of reaeartk^ largely for the Hnlowax Corporation to only that one material adopted with otl known chlorinated compounds to meet tb4 requirements of customers? That is om^ of the foolish ones probably, but I sbstj just ask it.
Furthermore, how long is it reaaonablst expect the liver to recover after it has beets*] pretty well damaged. I talked to you you anid you hadn't worked that out the animals as yet.
Dr. Cecil K. Drinker: In that case ' set aside a certain number of animals recover, after knowing that a certify amount of damage had been done. They we started to kill them but wc invariably ran out of rats before they rnn out of lesiooM
We don't know how long it lasts.
Dr. H. L. Vositrur.it: Have you
them cnlcium and glucose ns you would witaj
carbon tetrachloride?
Dr. Cecil K. Drinker: Not yet, but' ^ are doing an experiment now with one grouP^ on a very high calcium diet and ano group on a calcium free diet. The wh ^ question of calcium in the diet, of
w0milk daily to these people may be
while.
!* D*esmtio
'Wtl %*'
->i.do40 /I'"""
WATER PCB-SD0000056649
EFFECTS OF CHLORINATED HYDROCARBONS
311
%!* g_ L. Vosbcrou: I just had those
M jn mind. I would like to hear
';^It Mf- Brown would say as to the possiof using only this one innocuous
;'i\ naphthalene.
gANDFORD Brown: That would
BwWy our Problem exceedingly, not only (ie commercial standpoint but from
.`i (oxicity standpoint. But if we did so tfciek that Mr. Kaimer would be the first
because he wouldn't be able to get
&t taehnical effects he desires in the cable, eame thing applies throughout all the
where we are using these higher
.-' tfeferiaated products. Th problem as we see it, and it is one we intend to study further (we have
"(jar program for this continuous work that
be done under the direction of the
* Brisker brothers), is to try to find a line of
(. Aaureation and whether or not within this
Hit^Bpilcated chemical structure there is
one thing that causes the trouble. If
^.;,W Could take hexachlornaphthalene and g^WBOte 1 per cent of some unknown constit-
rt*at with which we are not now familiar
eliminate the toxicity, that would be tferdy solution. Whether we will ever be
I' to attain that I don't know. That i3
lof the things we have in mind.
`A, 1 "Id before, that is one of the things ^Biti which all manufacturers of these syn-
r-, ^(tie organic products are confronted at
** stage, either in their laboratories or in
^CWUnercial developments. It is largely a *P*tion of timing as to when you should do ^ Work, how much you should do, and
fther you know how to do it. You have
fcarn that first.
*
. Cecu, K. Drinker: Unless there is
.. sother important matter I will declare .^1 meeting adjourned.
MTv- .
R. Savers: May I say a word -"BWith regard to what Dr. Hookey stated
syphilis? If you arc going to eliminate
your workers who happen to develop
syphilis during the time they are working for you, you are probably going to lose some very important employees. It would seem that it would be worth while to give serious consideration to seeing that conditions arc proper and suitable for them to continue working for you and that they have proper treatment. In other words, I don't believe that is a good or sufficient reason for dis charging those employees who do develop syphilis. We have not found that to be true in other places and I question whether this is one of the places. I may be in error.
Mr. Sandford Brown: I want to take this occasion to express on behalf of the Halowax Corporation my thanks for the excellent cooperation we have received from various state authorities and our customers as well in this investigation. I believe you have all formed the opinion, based on what you have heard this morning, that our whole motive here is to conduct this on an ethical, scientific and constructive basis.
In collaboration with the Monsanto Chemical Company wc have a much more comprehensive program in view to carry on. Therefore we want to continue that same type of cooperation.
There is one thing that I want to bring up in that connection, which will have to be observed by the state authorities, when they go out to make these inspections. That m the necessity of not creating mob hysteria on the part of the workmen in the plants where these inspections are made. Mr. Hemperiy has run into some very interest ing situations in the various examinations lie has made. I know that lie would be glad to relate them and give the benefit of his experience to the heads of any of these state departments who will have the direction ot this work. Otherwise 1 can see where wc will be unable to get the full cooperation of not only the individual workmen but the plant foremen and the management, and we must have that if we are to get the results that we are shooting for over the next sev eral months or years. This thing may con tinue, probably will continue for years.
I'.faliSciniO INDUSTRIAL CHEMICALS CO.
*.'.* iNmi *, i.nt
R. E. Keller - TIB - St. Louis
August 15, 1975
CHLORINATED DIBENZO
TO R. Baxter LLN - 5045
B2S1.
LLN - 5045 T2F TIB B2SK T3A B2SD
Dick
In June this year a plan was developed with Bill Papageorge and others
to learn more about chlorinated dibenzofurans in our Aroclor products.
As a part of this plan it was decided that furans standards should be
.
prepared and analytical methodology developed for the detection of at
least 0.1 ppm for each furan homolog. Laboratory mixtures of monochloro-
through hexachlorodibenzofurans have been prepared and characterization
for homolog distribution is underway. Also, we have about one-man con
tinuous effort on the method development work.
As part of the plan it was decided that we should determine if Bayer has carried out "in-house" work of this type. The attached June 16 memo from Dave Wood to J. N. Haggart covers a request for this information. We have had no reply to this correspondence to our knowledge. Any infor mation or assistance you can provide on this point will be appreciated.
During the past week a publication has appeared in the literature entitled "Identification of Chlorinated Dibenzofurans in American Polychlorinated
Biphenyls" by R. W. Risebrough et al. of the University of California. A copy of this paper is attached. It shows the identification of chlori nated dibenzofurans in our Aroclor products except Aroclor 1016. We are now anxious to develop our own data for comparison with this publication.
Regards
ss Attachments(2)
R. E. Keller
NEV 021408
v PLAINTIFF'S 1
Hh kEXXHItBIT
I in 7
I
729463
WATER PCB-SD0000056651
Monsanto
i -Gladys Burgos - N. Y. 0.
'.A (I February 10, 1975
MM* || |
WESTINGHOUSE
HMW| l* |
TO C. R. Field
H. R. Ford* T. L. Gossage
Jordan t M. L'. Marcum
D. L. Mellon
C. Paton** M. A. petrilli D. A. Rutherford P. ho Slayton
D. Wood
Attached is a xerox copy of the Westinghouse Codicil No. 1 which is part of the contract. Please attach this to your copy of the contract.
Thanks.
t G
* Original carbon copy. ** Original copy.
NEV 006406 705642
WATER PCB-SD0000056652
Mom unto
MONSANTO INDUSTRIAL CHEMICALS CO. 1114 Avenue o( the Artiot>cis New York, Now Voik 10036 Phono: (212) 764-5000 .
CODICIL NO. 1
February 3, 1975
Westinghouse Electric Corporation Box 920 - Highway 58 West South Boston, Virginia 24592
Gentlemen:
This letter is codicil to contract on Inerteen 54201 CM dated January 6, 1975, and should be considered a part of it.
It is understood that the products sold hereunder contain polychlorinated biphenyls, which some studies have shown may' be an environmental contaminant. Buyer agrees to use its best efforts to prevent such products from entering into the environment through spills, leakage, use, disposal, vaporiza- , tion, or otherwise. In the event Seller determines that, in order to prevent an unreasonable threat to health or the environment, it is necessary to discontinue the sale to Buyer of polychlorinated biphenyls for the applications contemplated by Buyer, Seller may terminate the Agreement at any time by giving Buyer at least ninety (90) days' prior written notice.
Because of potential toxicological and/or ecological conse quences, Inerteen 54201 CM should not be used or purposely contaminated with other materials such as chlorinated naphthalenes or chlorinated alkyl naphthalenes or chlorinated alkyl biphenyls. In the event of any such use or contamination, this contract may be terminated by Seller within thirty (30) days' notice, (Does not apply to trichlorobenzene as commercially used in transformer fluids.)
ACCEPTED BY:
criteria for a recommended standard --
OCCUPATIONAL EXPOSURE TO
POLYCHLORINATED BIPHENYLS (PCBs)
U.S. DEPARTMENT OF HEALTH, EDUCATION, AND WELFARE Public Health Service
Center for Disease Control National Institute for Occupational Safety and Health
SEPTEMBER 1977 :04O2F or sale by the Superintendent of Documents U.S. Government
Printing Office . Washington. D.C .
GENP 006894
775298
WATER PCB-SD0000056654
WATER PCB-SD0000056655
PREFACE
The Occupational Safety and Health Act of 1970 emphasizes the need for standards to protect the health and safety of workers exposed to an ever-increasing number of potential hazards at their workplace. The National Institute for Occupational Safety and Health has projected a formal system of research, with priorities determined on the basis of specified indices, to provide relevant data from which valid criteria for effective standards can be derived. Recommended standards for occupational exposure, which are the result of this work, are based on the health effects of exposure. The Secretary of Labor will weigh these recommen dations along with other considerations $uch as feasibility and means of implementation in developing regulatorv standards.
It is intended to present successive reports as research and epide miologic studies are completed and as sampling and analytical methods are developed. Criteria and standards will be reviewed periodically to ensure continuing protection of the worker.
I am pleased to acknowledge the contributions to this report on polychlorinated biphenyls by members of the- NIOSH staff and the valuable, constructive comments by the Review Consultants on polychlorinated biphenyls, by the ad hoc committees of the Society for Occupational and Environmental Health.and the American Occupational Medical Association, and
GENP 006896
iii
^^5299 WATER PCB-SD0000056656
by Robert B. O'Connor, M.D., NIOSH consultant in occupational medicine. The NIOSH recommendations for standards are not necessarily a consensus of all the consultants and professional societies that reviewed this criteria document on polychlorinated biphenyls. A list of Review Consultants appears on page vi.
`Sob.Ti.J? . rinklea, M.D. Di^ctor, National Institute for
Occupational Safety and Health
iv
GENP 006897
WATER PCB-SD0000056657
The Division of Criteria Documentation and Standards Development (DCDSD), National Institute for Occupational Safety and Health, had primary responsibility for the development of the criteria and recommended standard for polychlorinated biphenyls. From DCDSD, John H. Fajen served as criteria manager and developed the basic information with the assistance of John A. Wass, Ph.D, Personnel from other NIOSH Divisions that assisted in the development of this document were Robert H. Hill Jr., Ph.D., Alan K. Gudeman, and Dennis M. 0'Brien (Division of Physical Sciences and Engineering); Mark W. Jones (Division of Surveillance, Hazard Evaluations and Field Studies); and Trent R. Lewis, Ph.D. (Division of Biomedical and Behavioral Science).
The DCDSD review of this document was provided by Richard A.
Rhoden, Ph.D., Chairman; J. Henry Wills, Ph.D.; and Howard
L. McMartin, M.D., with A. Blair Smith, M.D. (Division of
Surveillance, Hazard Evaluations and Field Studies), and
James H. Sterner, M.D.
'
The views expressed "in this document, the conclusions reached, and the recommendations for a standard are those of NIOSH after review of the evidence and consideration of the comments of reviewers. These views and conclusions are not necessarily those of the consultants, other federal agencies, and professional societies that reviewed the document.
GENP 006898
v
775300 WATER PCB-SD0000056658
NIOSH REVIEW CONSULTANTS ON POLYCHLORINATED BIPHENYLS
Mary Bell, Ph.D. Department of Environmental Health University of Cincinnati Cincinnati, Ohio 45267
Eula Bingham, Ph.D. Department of Environmental Health University of Cincinnati Cincinnati, Ohio 45267
Rudolph J. Jaeger, Ph.D. Department of Physiology School of Public Health Harvard University Boston, Massachusetts 02115
'
Carl C. Smith, Ph.D.
Department of Environmental Health
University of Cincinnati
'
Cincinnati, Ohio 45267
James R. Allen, DVM, Ph.D. Department of Pathology University of Wisconsin Medical School Madison, Wisconsin 53706
Paul E..Brubaker, Ph.D. Mobil Oil Corporation Paulsboro, New Jersey 08066
Renate D. Kimbrough, M.D. Bureau of Laboratories Center for Disease Control Atlanta, Georgia 30333
David Kotelchuck, Ph.D. United Electrical, Radio,
and Machine Workers of .America New York, New York 10007
-
Charles E. Lawrence, Ph.D. New York State Department of Health Albany, New York 12237
William B. Papageorge Monsanto Industrial Chemicals Company St. Louis, Missouri 631th
GENP 006899
WATER PCB-SD0000056659
CRITERIA DOCUMENT: RECOMMENDATIONS FOR AN OCCUPATIONAL EXPOSURE STANDARD FOR POLYCHLORINATED BIPHENYLS
Table of Contents
Page
PREFACE
. ill
NIOSH REVIEW CONSULTANTS
vi
I. RECOMMENDATIONS FOR A POLYCHLORINATED BIPHENYLS (PCBs) STANDARD
I
Section 1 - Environmental (Workplace Air)
Section 2 - Medical
Section 3 - Labeling and Posting
Section 4 - Personal Protective Equipment and Clothing
Section 5 - Informing Employees of Hazards from PCBs
Section 6 - Work Practices and Engineering Controls
Section 7 - Sanitation Practices
1
Section 8 - Monitoring and Recordkeeping Requirements
3 3 5 6 8 10 14 15
II. INTRODUCTION , 19
III. BIOLOGIC EFFECTS OF EXPOSURE
21
Extent of Exposure
Metabolism and Mechanism of Action
Historical Reports
Effects on Humans
Epidemiologic Studies
Animal Toxicity
Correlation of Exposure and Effect
Carcinogenicity, Mutagenicity, Teratogenicity,
Effects on Reproduction
and
21 27 31 33 54 66 105 116
IV. ENVIRONMENTAL DATA AND BIOLOGIC EVALUATION
126
Environmental Concentrations Control of Exposure Environmental Sampling and Analytical Methods Biologic Evaluation
126 132 133 144
V. WORK PRACTICES
145
GENP 006900
vii .
,,
775301
WATER PCB-SD0000056660
Table of Concents (Continued)
VI. DEVELOPMENT OF STANDARD Basis for Previous Standards Basis for the Recommended Standard
VII. RESEARCH NEEDS VIII. REFERENCES
IX. APPENDIX I - Sampling Procedure for Collection of Polychlorinated Biphenyls
X. APPENDIX II - Analytical Method for Polychlorinated Biphenyls
XI. APPENDIX III - Material Safety Data Sheet XII. TABLES
Page 148 148 152 164 166
191
196 208 218
viii.
GENP 006901
WATER PCB-SD0000056661
I. RECOMMENDATIONS FOR a POLYCHLORINATED BIPHENYLS (PCBs) STANDARD
The National Institute for Occupational Safety and Health (NIOSH)
recommends that employee exposure to polychlorinated biphenyls (PCBs) in
the workplace be controlled by adherence Co the following sections. The
standard is designed to protect the health and provide for the safety of
employees for up to a 10-hour workday, 40-hour workweek, over a normal
working lifetime. The standard is measurable by techniques that are valid,
reproducible, and available to industry and governmental agencies.
Compliance with the standard should substantially reduce any risk of
reproductive or tumorigenic effects of PCBs and prevent other adverse
effects of exposure in the workplace. Employees should regard the
recommended workplace environmental limit as the upper boundary for exposure
and make every effort to keep exposure as low as possible.
Evidence indicates adverse reproductive and tumorigenic effects in
experimental animals exposed to certain commercial PCB preparations.
Currently available information is not adequate to demonstrate that other
commercial PCB preparations do not have these effects. Should sufficient
information become available to indicate that the standard offers greater
or lesser protection from some chlorobiphenyl isomers or commercial
preparations than is needed, it will be considered for revision.
The Toxic Substances Control Act of 1976 (Public Law 94-469) required
the US Environmental Protection Agency (EPA) to prescribe marking and
disposal regulations for PCBs by July 1, 1977 (Federal Register 42:26563
77, May 24, 1977) .
By this Act, the manufacture, processing,
_i
distribution
GENP 006902
WATER PCB-SD0000056662
in commerce, or use of PCBs in any but totally enclosed systems is to be banned, effective 1 year after the date of its enactment, October 11, 1976, Two years after the enactment date PCB manufacture is to be banned, and processing and distribution in commerce are to be banned 2.5 years from that date. However, the Act allows the Administrator of EPA to rule otherwise if he finds that manufacture, processing, distribution in commerce, or use in other than totally enclosed systems will not present an unreasonable risk of injury to health or to the environment. The'Act does not affect use of equipment already containing PCBs in totally enclosed systems, so that a potential for occupational exposure to PCBs will continue to exist for many years as a consequence of their transportation, installation, use, and disposal. The part of the Act specific for PCBs is presented in Figure 1-1.
"PCBs" are defined for this recommended standard as commercial preparations of chlorinated biphenyl compounds, including those preparations which may be described as single isomers or classes of isomers, such as Decachlorodipheny1. Biphenyl and its monochlorinated derivatives occurring in commercial preparations of PCBs shall be measured along with the polychlorinated derivatives, and shall be treated in this standard as the polychlorinated components of the preparations.. "Occupational exposure to PCBs," is defined as working with PCBs or with equipment containing PCBs that can become airborne or that can spill or splash on the skin or into the eyes', or the handling of any solid products that may result in exposure to PCBs by skin contact or by Inhalation. The term "PCB work area" is defined as an area where there is occupational exposure to PCBs. In areas where no occupational exposure to PCBs occurs,
2
775303
GENP
WATER PCB-SD0000056663
bUC where PCBs are present in equipment in the workplace, adherence is required only to Section 8(a).
Section 1 - Environmental (Workplace Air) (a) Concentration Occupational exposure to polychlorinated biphenyls (PCBs) shall be
controlled so that no worker is exposed to PCBs at a concentration greater than 1.0 microgram total PCBs per cubic meter of air (1.0 yg/cu m), determined as a time-weighted average (TWA) concentration, for up to a 10hour workday, 40-hour workweek.
(b) Sampling and Analysis The recommended TWA occupational exposure limit for PCBs has been determined to be the lowest reliably detectable limit by the sampling and analytical methods recommended in this document. Environmental samples shall be collected and analyzed as described in Appendices I and II, or by any methods shown to be at least equivalent in accuracy, precision, and sensitivity to the methods specified.
Section 2 - Medical Medical surveillance shall be made available to all employees subject
to occupational exposure to PCBs. (a) Preplacement or initial medical examinations for workers shall
include: (1) Comprehensive medical and work histories with special
emphasis on hepatic function, skin condition, and reproductive history.
3
GENP 006904
775304
WATER PCB-SD0000056664
(2) Comprehenaive physical examination with particular
attention to the skin and to hepatic function including determinations of
serum glutamic-oxaloacetic transaminase (SCOT) and serum glutamic-pyruvic
transaminase (SGPT) activities. The responsible physician may also wish to
obtain measurements of serum triglyceride concentrations or of other
indices of fat metabolism.
(3) A Judgment of the employee's ability to use positive
pressure respirators.
(b) During examinations, applicants or employees having medical
conditions that could be directly or indirectly aggravated by exposure to
polychlorinated biphenyls or formulations containing polychlorinated
biphenyls shall be counseled on the Increased risk of impairment of their
health that might result from working with these substances.
(c) Women in the work force who are of child-bearing age shall be
advised of the potential adverse effects of PCBs on the unborn child.
Those who bear children while working with PCBs shall be counseled
concerning the advisability of nursing their babies.
(d) Initial medical examinations shall be made available .to all
workers as soon as practicable after promulgation of a standard based on
these recommendations.
..
(e) Periodic examinations shall be made available at least annually and Include: (1) interim medical and work histories, and (2)
physical examinations as outlined in paragraphs (a)(1) and (a)(2) of this section.
(f) If evidence of adverse effects of exposure to PCBs is
suspected or confirmed, appropriate medical care shall be made available to
the affected worker(s).
U
775305
GENP 006905
WATER PCB-SD0000056665
(g) Pertinent medical records shall be maintained for all employees exposed to PCBs in the workplace. Such medical records shall be maintained for the period of employment plus 30 years. These records shall be made available to the designated medical representatives of the Secretary of Health, Education, and Welfare, of the Secretary of Labor, of the employer, and of the employee or former employee.
Section 3 - Labeling and Posting
All labels and warning signs shall be printed both in English and in
the predominant language of non-English-reading workers.
Illiterate
workers and workers reading languages other than those used on labels and
posted signs shall be otherwise informed regarding hazardous areas and
shall be informed of the instructions printed on labels and signs.
(a) Labeling
The following warning label shall be affixed in a readily visible
location on PCB-processing or other equipment, and on PCB-storage tanks or
containers:
POLYCHLORINATED BIPHENYLS ' (PCBs)
DANGER! CONTAINS POLYCHLORINATED BIPHENYLS CANCER SUSPECT AGENT
Use only with adequate ventilation. Do not get in eyes, or on skin or clothing.
First Aid: In case of skin or eye contact, flush with running water.
GENP 006906
775306
WATER PCB-SD0000056666
(b) Posting Warning placards shall be affixed in readily visible locations in cr near PCB work areas, The information contained thereon shall be arranged as in the following example.
POLYCHLORINATED BIPHENYLS (PCBs) DANGER!
CANCER SUSPECT AGENT AUTHORIZED PERSONNEL ONLY
Do not enter unless area is adequately ventilated. . Do not get in eyes, or on skin or clothing.
First Aid: In case of skin or eye contact, flush with running water.
Section 4 - Personal Protective Equipment and Clothing (a) Protective Clothing In any operation where workers may come Into direct contact with
PCBs, protective clothing impervious to PCBs shall be worn. Gloves, boots, overshoes, and bib-type aprons that cover boot tops shall be provided when necessary. Protective apparel shall be made of materials which most effectively prevent skin contact with PCBs where it is most likely to occur. Employers shall ensure that all personal protective clothing is inspected regularly for defects and that it is in a clean and satisfactorv condition. -
(b) Eye Protection Chemical safety goggles, face shields (8-Inch minimum) with goggles, or safety glasses with side shields shall be provided by employers and shall be worn during any operation In which PCBs are present. If licuid or
6
775307
GENP 006907
WATER PCB-SD0000056667
solid PCBa contact the eyes, the eyes shall be Irrigated Immediately with large quantities of water and then examined by a physician or other responsible medical personnel. (A drop of vegetable oil on the eye has been found to reduce the resultant irritation.) Eye protection shall be in accordance with 29 CFR 1910.133 and ANSI Z 87.1-1968.
(c) Respiratory Protection (1) Engineering controls shall be used when needed to keep
concentrations of airborne PCBs at or below the recommended TWA occupational exposure limit. The only conditions under which compliance with the permissible exposure limit may be achieved by the use of respirators are:
(A) During the time necessary to install or test the required engineering controls.
(B) For nonroutine maintenance or repair activities. (C) During emergencies when concentrations of airborne PCBa may exceed the permissible limit. (2) When the use of respirators is permitted by paragraph c(l) of this section, respirators shall be selected and used in accordance with the following requirements: (A) The employer shall establish and enforce a respiratory protection program meeting the requirements of 29 CFR 1910.134. - (B) The employer shall provide respirators in accordance with Table 1-1 and shall ensure that employees properly use the respirators provided. The respirators shall be those approved by NIOSH or the Mining Enforcement and Safety Administration. The standard for approval is specified in 30 CFR 11. The employer shall ensure that
GENP 006908
7
775308
WATER PCB-SD0000056668
respirators are properly cleaned, maintained, and stored when not in use.
TABLE 1-1 RESPIRATOR SELECTION GUIDE
Concentration of PCBa
Greater than 1.0 ^g/cu m or Emergency (entry into area of unknown concentra tion)
Respirator Type Approved under Provisions of 30 CFR 11
(1) Self-contained breathing apparatus with full facepiece operated in pressure-demand or other positive pressure mode.
(2) Combination Type C supplied-air respirator with full facepiece operated in pressure-demand or other positive pressure mode and an auxiliary self-contained breathing apparatus operated in pressure demand or other positive pressure mode.
Section 5 - Informing Employees of Hazards from PCBs
(a) All new and present employees in any area in which PC3s are
used shall be informed of the hazards, relevant symptoms, and effects cf
overexposure to PCBs, and the precautions to be observed for safe use and
handling of these materials.
.
. (b) 'All employees involved with the manufacture, use, transport,
or storage of PCBs shall be informed that PCBs have been found to induce
tumors in experimental animals after repeated oral ingestion and that
because of these findings it is concluded that PCBs are potential human
carcinogens; employees shall also be informed chat adverse reproductive
8 775309
GENP 006909
WATER PCB-SD0000056669
effects may result from occupational exposure to PCBs. (c) The employer shall institute a continuing education program,
conducted by instructors qualified by experience or training, to ensure that all employees occupationally exposed to PCBs have current knowledge of job hazards, proper maintenance and cleanup methods, and proper use of protective clothing and equipment, including respirators. The instructions shall include a general description of the medical surveillance program and of the advantages to the employee of participation. Special attention shall be given to women in the workplace. They shall be made aware of the potential adverse effects of PCBs on the unborn child, and of the known transport of PCBs to breast milk. Elements of the program shall also include:
Emergency procedures and drills; Instruction in handling spills and leaks; Decontamination procedures; Firefighting equipment location and use; First-aid procedures, equipment location, and use; Rescue procedures; Confined space entry procedures; Low warning (odor) properties of PCBs.
-
(d) The information explaining the hazards of working with PCBs shall be kept on file and be readily accessible to workers at all places of employment where PCBs are manufactured, used, stored, or transported. Required information shall be recorded on the "Material Safety Data Sheet" shown in Appendix III, or similar form approved by the Occupational Safety and Health Administration, US Department of Labor.
GENP 0069JO
9
775310
WATER PCB-SD0000056670
Section 6 - Work Practices and Engineering Controla
(a) Regulated Areas
Access to PCB work areas shall be regulated and limited to authorized
persons. A daily roster shall be kept of persons entering such areas.
(b) Handling of PCBs and General Work Practices
(1) Operating instructions shall be formulated and posted
where PCBs are handled or used.
,
(2) Transportation and use of PCBs shall comply with all
applicable local, state, and federal regulations.
(3) PCBs shall be stored in tightly closed containers ir.
well-ventilated areas.
(4) When PCB storage containers are being moved, or when
they are not in use and are disconnected, valve protection covers shall he
in place. Containers shall be moved only with the proper equipment sr.:
shall be secured to prevent dropping or loss of control during transport.
(5) Storage facilities shall be designed to contain spills
completely within surrounding dikes and to prevent contamination of
workroom air.
(6) Ventilation switches and emergency respiratcrv
equipment shall be. located outside storage areas in readily accessible
locations which will remain minimally contaminated with PCBs in =.r.
emergency.
(7) Process valves and pumps shall be readily accessible
and shall not be located in pits or congested areas.
' (8)
Containers and systems shall be handled and opened wt:-
care. Approved protective clothing as specified in Section 1 shall he vcr-
10
GENP 006911
775311
WATER PCB-SD0000056671
by employees engaged in opening, connecting, and disconnecting PCB
containers and systems. Adequate ventilation shall be provided to minimize
exposures of such employees to airborne PCBs.
(9) PCB-operating and storage equipment and systems shall
be Inspected daily for signs of leaks. All equipment, including valves,
fittings, and connections shall be checked for leaks Immediately after PCBs
are introduced therein.
'
(10) When a leak is found, it shall be repaired or otherwise
corrected immediately. Work shall resume normally only after necessary
repair or replacement has been completed, the area has been ventilated, and
the concentration of PCBs has been determined by monitoring to be at or
below the recommended TWA concentration limit.
(c) Control of Airborne PCBs
(1) Suitable engineering controls, designed to maintain
exposure to airborne 'PCBs at or below the limit prescribed in Section 1(a),
shall be used. Complete enclosure of processes is the recommended method
for control of PCB exposure. Local exhaust ventilation may also be
effective, used alone or in combination with process enclosure. When a
local exhaust ventilation system is used, it shall be so designed and
operated as to prevent accumulation or recirculation of airborne PCBs in
the workplace environment and to effectively remove PCBs from the breathing
zones of employees. Exhaust ventilation systems discharging to outside air
must conform to applicable local, state, and federal regulations and- must
not constitute a hazard to employees or to the general population. Before
maintenance work on control equipment begins, the generation of airborne
PCBs shall be eliminated to the extent feasible.
GENP 006912
11
775312
WATER PCB-SD0000056672
Enclosures, exhaust hoods, and ductwork shall be kept in good repair
so that designed airflows are maintained. Airflow at each hood shall be
measured at least semiannually and preferably monthly. Continuous airflow
indicators are recommended, such as water or oil manometers properly
mounted at the juncture of fume hood and duct throat (marked to indicate
acceptable airflow). A log shall be kept showing design airflow and the
results of semiannual airflow measurements.
'
(2) Forced-draft ventilation systems shall be equipped with
remote manual controls and shall be designed to shut off automatically in
the event of a fire in the PCB work area.
(d) Special Work Areas
(1) PCB Hazard Areas
A hazard area shall be considered as any space having physical
characteristics and containing sources of PCBs, such as transformers, that
could result in PCB concentrations in excess of the recommended airborne
PCB exposure limit. Exits shall be plainly marked, conveniently located,
and open outwardly into areas which will remain minimally contaminated in
an emergency.
(2) Confined or Enclosed Spaces
Entry into confined or enclosed spaces, such as tanks, pits,
process vessels, and tank cars where there is limited egress, shall be
controlled by a permit system. Permits shall be signed by an authorized
representative of the employer and shall certify that appropriate measures
have been taken to prevent adverse effects on the worker's health as a
result of his or her entry into such space.
-
775313
12
GENP006913
WATER PCB-SD0000056673
Confined or enclosed spaces which have contained PCBs shall be thoroughly ventilated to assure an adequate supply of oxygen, tested for PCBs and other contaminants, and inspected for compliance with these requirements prior to each entry. Adequate ventilation shall be maintained while workers are in such spaces. Leakage of PCBs into such confined or enclosed spaces while work is in progress shall be prevented by disconnecting and blanking the PCB supply lines. Each individual entering such confined or enclosed space shall be furnished with appropriate personal protective equipment and clothing and be connected by a lifeline harness to a standby worker stationed outside of the space. The standby worker shall also be equipped for entry with approved personal protective equipment and clothing and have contact with a third person. The standby person shall maintain communication (visual, voice, signal line, telephone, radio, or other suitable means) with the employee inside the confined or enclosed space.
(e) Emergency Procedures For all PCB work areas where there is a potential for the occurrence of emergencies, employers shall take all necessary steps to ensure that employees are instructed in, and follow, the procedures specified below as well as any others appropriate to the specific operation or process.
(1) If PCBs leak or are spilled, the following steps shall be taken:
(A) All nonessential personnel shall be evacuated from the leak or spill area.
(B) The area of the leak of spill shall be adequately entilated to prevent the accumulation of vapors.
GENP 006914
13
775314
WATER PCB-SD0000056674
(C) If the PCBa are in liquid form, they shall De collected for reclamation or sorbed in vermiculite, dry sand, earth, or similar nonreactive material.
(2) Personnel entering the spill or leak area shall be furnished with appropriate personal protective equipment and clothing. All other personnel shall be prohibited from entering the area.
(3) Only personnel trained in the emergency procedures and protected against the attendant hazards shall shut off sources of PCBs, clean up spills, control and repair leaks, and fight fires, in areas where PCBs are used.
(4) All wastes and residues containing PCBs shall be collected in PCB-reaiatant containers and appropriately disposed of (Federal Register 42:26563-77. May 24, 1977).
(5) Safety showers, eyewash fountains, and washroom facilities shall be provided, maintained in working condition, and located
a
so as to be readily accessible to workers in all areas where the occurrence of skin or eye contact with PCBs is likely. If liquid or solid PCBs are splashed or spilled on an employee, contaminated clothing shall be removed promptly and the skin washed thoroughly with soap and water for at least 15 minutes. Eyes shall be irrigated immediately with copious quantities of running water for at least 15 minutes if liquid or solid PCBs get into them. A drop of vegetable oil may be applied to the eye to relieve the irritating effect of PCBa.
Section 7 - Sanitation Practices (a) Employees occupationally exposed to PCBs shall be provided
14 775315
.
GENP 006915
WATER PCB-SD0000056675
with separate lockers or other storage facilities for street clothes and
for work clothes. (b) Employees occupationally exposed to PCBs shall not wear work
clothing away from their place of employment.
(c) Employees occupationally exposed to PCBs shall be provided
clean work clothing daily, and cleaning establishments shall be informed as
to the hazards of handling PCBs and proper disposal procedures for PCB-
contaminated waste water.
..
(d) Facilities for shower baths shall be provided for employees
occupationally exposed to PCBs. Workers should shower before changing into
street clothes.
(e) Employees exposed to PCBs shall be advised to wash their hands
and exposed skin before eating, drinking, smoking or using toilet
facilities during the work shift.
(f) Food, drink, or smoking materials shall not be permitted in
areas where PCBs are handled, processed, or stored.
Section 8 - Monitoring and Recordkeeping Requirements (a) Monitoring (1). As soon as practicable after the promulgation of a
standard based on these recommendations, each employer who manufactures, processes, handles, stores or otherwise uses PCBs shall determine by an industrial hygiene survey whether occupational exposure to PCBs may occur. Surveys shall be repeated at least once every year and within 30 days of any process change likely to result in occupational exposure to PCBs. Records of these surveys, including the basis for any conclusion that there
15
GENP 006916
775316
WATER PCB-SD0000056676
may be no occupational exposure to PCBs, shall be retained until the next
survey has been completed.
(2) If occupational exposure to PCBs is determined to be
possible, a program of personal monitoring shall be instituted to measure
or permit calculation of the exposures of all employees.
(A) In
all personal monitoring,
samples
representative of the employees' breathing zones shall be collected.
. (B)
For each TWA concentration determination, a
sufficient number of samples shall be taken to characterize each employee's
exposure during each work shift. Variations in work and.production
schedules and in employees' locations and job functions shall be considered
in choosing sampling times, locations, and frequencies.
(C) Each operation in each work area shall be
sampled at least once every 3 months.
(3) If an employee is found to be exposed to PCBs in excess
of the recommended TWA concentration limit, control measures shall be
initiated, the employee shall be notified of the exposure and of the
control measures being Implemented to correct the situation, and the
employee shall be monitored every 30 days. Such monitoring shall continue
until two such consecutive determinations indicate that the employee's
exposure no longer exceeds the recommended TWA concentration limit.
Routine monitoring may then be resumed.
(b) Recordkeeping
Environmental monitoring records shall be maintained for at least 30
years after the employee's last occupational exposure to PCBs. These
records shall include the dates and times of measurements, job function and
16 775317
GENP 006917
WATER PCB-SD0000056677
location of employees within the worksite, methods of sampling and analysts used, types of respiratory protection in use at the time of sampling, TWA concentrations found, and identification of exposed employees. Each employee shall be able to obtain information on his or her own environmental exposures. Daily rosters of authorized persons who enter regulated areas shall be retained for 30 years. Environmental monitoring records and entry rosters shall be made available to designated representatives of the Secretary of Labor and of the Secretary of Health, Education, and Welfare.
Pertinent medical records for each employee shall be retained for 30 years after the employee's last occupational exposure to PCBs. Records of environmental exposures applicable to an employee should be Included in that employee's medical records. These .medical records shall be made available to the designated medical representatives of the Secretary of Labor, of the Secretary of Health, Education, and Welfare, of the employer, and of the employee or former.employee.
GENP 006918
17
7 7S3l8 WATER PCB-SD0000056678
PUBLIC LAW 94-469--OCT. 11, 1976
90 STAT. 2025
(e) Poltchuirutated Biphenyls.--(1) Within six months after Rule*.
the effective date of this Act the Administrator shall promulgate
rules to--
(A) prescribe methods for the disposal of polychlorinated
biphenyls, and
(B) require polychlorinated biphenyls to be marked with clear
ana adequate warnings, and instructions with respect to their
processing, distribution in commerce, use, or disposal or with
respect to any combination of such activities.
Requirements prescribed by rules under this paragraph shall be con
sistent with the requirements of paragraphs (2) and (3).
a
(2) (A) Except as provided under subparagraph (13), effective one
year after the effective date of this Act no person may manufacture,
process, or distribute in commerce or use any polychlorinated biphenyl
in any manner other than in a totally enclosed manner.
(B) The Administrator may by rule authorize the manufacture,
processing, distribution in commerce or use (or any combination of
such activities) of any polychlorinated biphenyl in a manner other than
in a totally enclosed manner if the Administrator finds that such manu
facture, processing, distribution in commerce, or use (or combination
of such activities) will not present an unreasonable risk of injury to
health or the environment.
(C) For the purposes of this paragraph, the term "totally enclosed "Totallytfenclosed manner"' means any maimer which will ensure that any exposure of
human beings or the environment to a polychlorinated biphenyl will
be insignificant as determined by the Administrator by rule.
(3) (A) Except as provided in subparagraphs (B) and (C)--
(i) no person may manufacture any polychlorinated biphenyl
after two years after the effective date of this Act, and
(ii) no person may process or distribute in commerce any poly
chlorinated biphenyl after two and one-half years after such date.
(B) Any person may petition the Administrator for an exemption Petition for
from the requirements of subparagraph (A), and the Administrator exemption.
may grant by rule such an exemption if the Administrator finds
that--
(i) an unreasonable risk of injury' to health or environment
would not result, and
_
(ii) good faith efforts have been made to develop a chemical
substance which docs not present an unreasonable risk of injury
to health or the environment and which may be substituted for
such polychlorinated biphenyl.
An exemption granted under this subparagraph shall be subject to Terms and
such terms and conditions as the Administrator may prescribe and conditions.
shall be in effect for such period (but not more than one year from
tho date it is granted) as the Administrator may prescribe.
(C) Subparagraph (A) shall not apply to the distribution in com
merce of any polychlorinated biphenyl if such polychlorinated
biphenyl was sold for purposes other than resale before two and one
half years after the date of enactment of this Act.
(4) Any rule under paragraph (1), (2) (B), or (3) (B) shall be
promulgated in accordance with paragraphs (2), (3), and (4)-of sub
section (c).
..
(5) This subsection does not limit the authority of the Adminis
trator, under any other provision of this Act or any other Federal law,
to take action respecting any polychlorinated biphenyl.
FIGURE 1-1. SECTION 6(e) OF THE TOXIC SUBSTANCES CONTROL ACT 18
775319
GENP 006919
WATER PCB-SD0000056679
II. INTRODUCTION
This report presents the criteria and the recommended standard baaed thereon which were prepared to meet the need for preventing occupational disease and injury arising from workplace exposure to PCBs. The criteria document fulfills the responsibility of the Secretary of Health, Education, and Welfare, under Section 20(a)(3) of the Occupational Safety and Health Act of 1970, to "...develop criteria dealing with toxic materials and harmful physical agents and substances which will describe...exposure levels at which no employee will suffer impaired health or functional capacities or diminished life expectancy as a result of his work experience."
The National Institute for Occupational Safety and Health (NIOSH), after a review of data*and consultations with others, formalized a system for the development of criteria upon which standards can be established to protect the health and to provide for the safety of employees exposed to hazardous chemical and physical agents. Criteria and recommended standards should enable management and labor to develop better engineering controls resulting in more healthful work environments. Mere compliance with the recommended standard should not be used as a final goal.
These criteria for a standard for PCBs are part of a continuing series of criteria developed by NIOSH. The recommended standard applies to the processing, manufacture, and hand 1ing of PCBs as applicable under the Occupational Safety and Health Act of 1970. The standard was not designed for the population-at-large, and any application to situations other than occupational exposures is not warranted. It is intended to (1) protect
19
GENP 006920
775320
WATER PCB-SD0000056680
against acute and chronic PCB poisoning, (2) be measurable by techniques that are available to industry and official agencies, and (3) be attainable with existing technology.
The standard is designed to substantially reduce the risk of development of carcinogenic, adverse reproductive, hepatotoxic, and dermatologic effects. Since 1970, PCBs have been one of the more thoroughly investigated environmental and occupational hazards. Nevertheless, there are Important gaps in the knowledge of chronic exposure effects in man at low concentrations of PCBs. Important research needs include studies on the reproductive histories of women who have been exposed to PCBs, and quantitation of the dermal and respiratory absorption of different mixtures of PCBs. A better understanding is needed of the contaminants in commercial PCB preparations, particularly studies to determine the extent to which any chlorinated dibenzofurans in tissues of PCB-exposed American workers result from direct absorption or are derived from PCBs in the body. Another need is for an assessment of the hazards associated with the mobilization, during fasting or in other abnormal physiologic states, of PCBs stored in the body.
775321
20
GENP 006921
WATER PCB-SD0000056681
III. BIOLOGIC EFFECTS OF EXPOSURE
"vfent of Exposure Biphenyl (C 12H 10), diagrammed in Figure III-l, can be chlorinated
by replacing any or all of its hydrogen atoms with chlorine [1].
32
6' 5
5 2' 3 Figure III-l. BIPHENYL MOLECULE AND RING NUMBERING SYSTEM
Specific chlorobiphenyl molecules are designated by reference to the positions of the chlorine atoms according to the numbering scheme depicted in Figure III-l. The lowest possible numbers are assigned, and the phenyl moiety with the fewest chlorine atoms is assigned prime numbers [1,2]. Examples of the nomenclature used here are shown in Figure III-2.
Cl Cl Cl
3-chlorobiphenyl
2,2',3,4',5-pentachlorobiphenyl
Figure III-2. EXAMPLES OF NOMENCLATURE SYSTEM OF CHLOROBIPHENYL COMPOUNDS
There are three mono chlorobiphenyl compounds, 2-, 3-, and 4-
chlorobiphenyl. The 5- and 6-monochlorobiphenyls are identical to 3- and
2-monochlorobiphenyl, respectively.
There are 18 dichlorobiphenyl
GENP 006922
21
775322
WATER PCB-SD0000056682
compounds. The number of possible chlorobiphenyl isomers and the corresponding weight-percents of chlorine are presented in Table III-l.
TABLE III-l
NUMBER OF ISOMERS AND PERCENT CHLORINE FOR THE 10 CHLOROBIPHENYL (PCB) CLASSES
Chlorobiphenyl
Bnpirical Formula
No. of Isomers
Weight % Cl
mono di
tri tetra penta
hexa hepta
octa nona deca
C 12H9C1 C 12H8C1 2 C 12H7C1 3 C 12H6C1 4 C 12H5C1 5 C 12H4C1 6 C 12H3C1 7 C 12H2C1 8 C 12HC1 9 C 10C1 10
Adapted from reference 1
3 12 24 42 46 42 24 12
3 1
18.79 31.77 41.30 48.56 54.30 58.93 62.77 65.98 68.73 71.18
In the commercial synthesis of chlorobiphenyls, biphenyl is catalytically chlorinated with anhydrous chlorine; either iron filings or ferric chloride may be used as the catalyst [1]. The commercial preparations, commonly referred to as "PCBs," are isomeric mixtures. The weight-percent chlorine in commercial mixtures has generally varied between 21 and 68% and has been used to designate grades of commercial products. Commercial PCB products' manufactured in the US, Great Britain, and Japan have been marketed under the trade name "Aroclor" [1-3]. Several grades of Aroclor have been designated by numbers such as 1221, 1242, 1254, and 1260, where the last two digits represent the percent by weight of chlorine in
22
77S323
GENP 006923
WATER PCB-SD0000056683
dibenzofurans [17-23] and naphthalenes [18,19] . Concentrations of chlorinated dibenzofurans in various commercial PCB products are presented in Table III-2.
TABLE III-2
CHLORODIBENZOFURAN TYPES AND CONCENTRATIONS Gtg/g) IN COMMERICAL PCB PREPARATIONS
Mixture* di
tri
Chlorodibenzofurans
tetra
penta
hexa hepta Total Ref.
(1) 1016 (1) 1016 (1) 1248 (1) 1254 (1) 1254 (1) 1260 (1) 1260 (2) A-60
(3) DP-6 (4) K300
(4) K400
(4) K500
(4) K600
0.5 (c)*** (e)
<0.001 0.5 0.1 0.2 0.1 0.2 1.4 0.7 (a) (e)
(a)
<0.001 1.2 0.2 0.4 0.4 0.3 5.0
10.0 (a) (c) (a) (a)
<0.001 0.3 1.4 0.9 0.5 0.3 2.2 2.9
(c) (a) (b) (b)
0.5
2.0 1.7 1.5 1.0 0.8 8.4 13.6 1-1.5 17-18 2.5-4 3-5
**
21 21 21 21 21 21 21 21 20 20 20 20
*(1) Aroclor, (2) Clophen, (3) Phenoclor, (4) Kanechlor **(I Pomeranez, written comDunlcation, January 1977) *** (a), (b), (c), (d), (e) represent relative amounts in increasing order
Some commercial preparations that were marketed under the trade name Aroclor contained chlorinated terphenyls in addition to chlorinated biphenyls. Aroclors 2565 and 4465 contained 75% and 602 chlorinated biphenyl compounds and 25% and 40% chlorinated terphenyl compounds, respectively. Both mixtures contained 65% chlorine [1].
A broad class of nonflacsnable synthetic chlorinated hydrocarbon insulating liquids used in electrical capacitors, transformers, nuclear
24 775324
. FLD 012393
WATER PCB-SD0000056684
the mixtures. Another grade of Aroclor, 1016, made primarily of tri- and
tetrachlorobiphenyl compounds and containing 41% chlorine by weight, waa
introduced in 1971 to replace Aroclor 1242 [2,4,5]. Other PCB products
manufactured in Japan were marketed as "Santotherm" [1], and "Kanechlors"
300, 400, 500, and 600, containing approximately 42%, 48%, 54%, and 60%
chlorine, respectively [6], In Germany, products marketed as "Clophens"
A50 and A60 contained 54 and 60% chlorine, respectively [7]. In Prance,
PCBs were marketed as "Phenoclors" and "Pyralenes;" Phenoclor DP6 contains
60% chlorine [8], Other countries reported to have produced PCBs are
Italy, Spain, Czechoslovakia, Poland, Argentina, Brazil, the USSR, and
India [1,9,10] .
The chlorobiphenyl constituents of several commercial PCB products
have been studied [6-8,11-16], Some data, both qualitative and
quantitative, are presented in Table XII-2. About half the 209 possible
chlorobipheryls do not occur in any of the commercial preparations. Among
those compounds which do not- occur, or which occur in trace amounts only,
are 3-chlorobiphenyl, all of the tri- to pentachloro compounds that are
chlorinated in only one ring, the penta-, hexa-, and heptachloro compounds
that are completely chlorinated in one ring, and the penta- and hexachloro
compounds that are chlorinated in four positions in one ring.
Commercial PCBs are insoluble in water, but are soluble in oil and
many organic solvents. Some other physical and chemical properties of
certain Aroclor products are presented in Table XII-1 [1].
In addition to chlorinated biphenyls, the commercial mixtures with
20-40% chlorine contained biphenyl from about 11% to traces, respectively,
by . weight.
Many commercial PCB products also contain chlorinated
GENP 006924
23
77537R
WATER PCB-SD0000056685
reactors, and accessory equipment is designated by the generic term
"askarel" [4,5,24,25]. PCBs have been major components of most askarels
used in the US since 1932. Two general classes of PCB-containing askarels
are "capacitor"-grade and "transformer"-grade [4,5]. Aroclor 1242 was the
major capacitor impregnant in the US before 1971; subsequently, Aroclor
1016 has been used mainly for this purpose [4]. Transformer-grade askarels
manufactured in the US include those marketed under trade names including
"Asbestol," "Chlorextol," "Inerteen," "No-Flamol," "Pyranol," and "Saf-T-
Kuhl" [4].
Transformer-grade askarels are . usually mixtures of
trichlorobenzene and more highly chlorinated (42-60%) biphenyls [5,24].
Some typical compositions are: 100% Aroclor 1242; 70% Aroclor 1254 and 30%
trichlorobenzene; 60% hexachlorobiphenyl and 40% trichlorobenzene; 45%
hexachlorobiphenyl and 55% trichlorobenzene; and 70%.pentachlorobiphenyl
and 30% trichlorobenzene. Another type of trans former-grad e askarel
contains 45% polychlorinated biphenyl (54% chlorine) and 55% of a mixture
of tri- and tetrachlorobenzenes. Transformer-grade askarels also contain
stabilizers such as glycidyl phenyl ether and 3,4-epoxycyclohexylmethyl-3,
4-epoxycyclohexane carboxylate [24].
Exposure to commercial preparations of PCBs in the work environment
may involve many different chlorinated biphenyl compounds, and also
substantial amounts of biphenyl, tri- and tetrachlorobenzenes, and small
amounts of many different chlorinated dibenzofurans, chlorinated
naphthalenes and in special uses, chlorinated terphenyls.
Commercial production of PCBs in the US began in 1929 and reached 85
million pounds in 1970 when the major producer began selling PCBs only for
use in "closed" systems. Since 1972, only those Aroclors designated 1016,
GENP 006925
25
77S326
WATER PCB-SD0000056686
.1221, 1242, and 1254 have been produced in Che US, and total annual production has been around 40 million pounds [26],
Imported PCBs amounted to about a half-million pounds in 1972 and 1973 [26,27]. A decachlorobiphenyl produced in Italy and imported by one company for use in investment casting waxes accounted for 80-90% of the total PCB imports [26], The other 10-20% was imported from France for use in semiclosed heat transfer applications [27], Occupational exposure to decachlorobiphenyl could occur in the manufacture of the investment casting waxes as well as in the preparation of the investment casting molds in the 25 US foundries which use the decachlorobiphenyl wax [26],
Most of the PCBs produced in the US since 1971 have been used in electrical capacitors (70%) and transformers (30%). About 95% of the 100 million capacitors produced annually in the US contain PCBs [27]. There is potential occupational exposure to PCBs in the plants of the 17 reported companies that manufacture capacitors in the US. Capacitors are generally classified into two categories for disposal purposes. "Small" capacitors contain less than 2 pounds of PCBs; those incorporated into electrical equipment such as television sets, home air conditioners, and light fixtures contain 2-340 ml of PCBs and have service lives of at least 10 years [26,28]. "Large" capacitors may contain about 25 liters of PCBs [26] and have a* service life of 15-20 years [26,27]. Potential occupational exposures exist in the servicing of appliances and in the disposal of used capacitors or equipment.
Transformers that contain PCBs are used mainly in or near inhabited buildings where fire hazards from cheaper oil-filled transformers are greatest. The estimated 135,000 PCB-containing transformers represent
775327 26 '
GENP 006926
WATER PCB-SD0000056687
about: 5% of all transformers in the US [27]. Occupational exposure to various askarels used for transformers may occur in their manufacture, servicing, and transportation, or as a result of leaks [29].
Other potential occupational exposures to PCBs exist through losses in storage [30] , shipment [29] , manufacture and use of heat exchange units [27.31], and in use of previously manufactured items which contain PCBs, such as hydraulic systems, vacuum pumps, and gas transmission turbines [30.31] . The past use of PCBs in carbonless copying papers may result in exposure of workers currently engaged in paper reclamation [30]. Workers in plants that previously used PCBs may have current exposure in their working environments because PCBs have been shown to remain in the workplace air and on surfaces for years after PCB use has been discontinued [32,33]. Several occupations that may have involved exposure to PCBs were tabulated in a 1966 publication [34]. NIOSH estimates that 12,000 workers have potential occupational exposure as a result of current uses of PCBs in their working environments [35].
In addition to their occupational exposures, PCB workers may be exposed to PCBs carried into their homes from the workplace [36], from general contamination of the ambient air [26,37,38] and water [26,37], and to PC3s and their metabolites in their diets [39-46].
Metabolism and Mechanism of Action A study of the metabolism of 4-chlorobiphenyl was reported in 1959 by
Block and Cornish [47]. In this experiment, 1 gram of 4-chlorobiphenyl was fed to rabbits in a single dose and 4'-chloro-4-biphenylol and its
GENP 006927
"
775328
WATER PCB-SD0000056688
glucuroniside were recovered from the urine in amounts that accounted for
24 and 50Z, respectively, of the administered dose.
Subsequently, a substantial number of metabolic studies of individual
chlorobiphenyl compounds [41-43,48-84] , mixtures [85,86], and metabolites
[48,49,87] were reported, and a comprehensive review was published in 1976
[88]. These reports collectively demonstrate through many study methods
that some aspects of metabolism are of special significance to the toxicity
of PCBs and that some isomers are more toxic, or have different effects,
than others [89-94].
Chlorinated biphenyl compounds are readily absorbed from the
digestive tract, regardless of the degree or pattern of chlorine
substitution [50,51,95,96]. It seems likely that similar absorptive
characteristics apply to the respiratory system since chlorobiphenyl
mixtures in air are rapidly absorbed [97], as is decachlorobiphenyl
[98,99]. Varying amounts of chlorobiphenyls, depending on degree and
pattern of chlorination, are excreted in the feces [42,50,53-56,100], milk
[41-44,51,101], and hair [102] of animals, but no more than trace amounts
are excreted in the urine [42,51-55,57-62,103-105].
Metabolites of chlorobiphenyl compounds have been found in the urir.e
of mammals including mice [52], rats [48,53-56,58-60,63,64,66,71,85],
rabbits [65,67-69], monkeys [51,61,74,75], swine [72], goats [73], and cows
[41,73], as well as in feces [48,50-54,56,58-65,76-80], and milk [41]. The
metabolites
excreted in urine [53,54,58,59,61,63,64,66,67], bile
[50,51,53,81], feces [52-54,58,63,76], and milk [41] are, to varying
degrees, conjugated with glucuronic or sulfuric acids. Differences in
metabolism of PCBs among the aforementioned species are more quantitative
775329 28
GENP 006928
WATER PCB-SD0000056689
chan qualitative [51,73]; however, metabolism in birds and fish may differ qua14tatively from that in mammals [55,77], Among mammals there are also
quantitative differences in PCB metabolism and in effects related to age
and sex [50,93,106]. Metabolites identified in mammals include mono- to
polyhydroxylated derivatives [41,48,49,51-56,58-81,85] , and methoxy
[59,60],
hydroxymethoxy
[64,65,68,70,76,87],
dihydrodihydroxy
,[51,53,54,69,74,75,81] , hydroxydihydrodihydroxy [51,74] , and dechlorinated
derivatives [48,65,70,77].
The lower-chlorinated biphenyl compounds are more readily metabolized
than are the more highly chlorinated ones [41,50,51,55,61-64,66,82
84,96,107-109] , with no metabolism having been demonstrated for
decachlorobiphenyl [66]. As a consequence, some of the more highly
chlorinated compounds persist in the tissues for years after intake has
been discontinued [51,83,103,110].
The presence of at least two adjacent, unsubstituted hydrogen atoms,
particularly in positions 3, 4, and 5, or 3', 4', and 5', is required for
rapid metabolism of chlorobiphenyls [79,83,84]. All mono- di-, and
trichlorobiphenyls, and all tetrachlorobiphenyls except 3,3',5,5'-
tetrachlorobiphenyl meet this requirement. The latter compound, 3,3* ,5 ,5'-
tetrachlorobiphenyl, was found to be particularly toxic to monkeys, and it
was suggested that the chlorinated dibenzofuran derivative may have been
involved [94]. While dibenzofuran derivatives have not been demonstrated
to exist as mammalian metabolites, they may have been identified as PCB
metabolites in chickens [111] and Curley et al [22] reported the excretion
of dibenzofurans in urine of rats. In the latter case, however,
dibenzofurans were also identified in the administered PCB [22].
GENP 006929
29
775330
WATER PCB-SD0000056690
Dibenzofurans are of concern because they may be many times more toxic than PCBs [19,112].
Metabolites found in urine [48,51,53,56,60,61,64,66-74,85], bile [81], feces [51-53,56,58,60,61,64,66,76,79,80,113], and milk [41] include hydroxy derivatives. Such compounds have been demonstrated to be more toxic than their respective parent chlorobiphenyl [41,114] and their presence in milk [41] is of special concern.
Hydroxylation may be direct through hydroxylating enzyme systems, or through formation of arene oxide intermediates [48,51,53,68,75,81,87,115]. This latter process is of particular concern because of potential carcinogenesis and mutagenesis as a result of covalent binding of arene oxides to nuclear components of the cell [51,68,74 ,82,86,116], Such binding has been demonstrated both in vivo [51,86] and in vitro [51,82,86,116,117]. Additional evidence of hydroxylation through arene oxide intermediates included findings of metabolites in which chlorine, dueterium, or tritium were at different molecular locations than in the administered compound [68,115,116,118], and transdihydrodiols as mammalian metabolites [51,69,74,75,81].
Although adjacent unsubstituted hydrogen atoms are necessary for rapid metabolism of chlorinated biphenyls, it has been demonstrated that 2,2',4,4',5,5'-hexachlorobiphenyl, which does not have this characteristic, can be hydroxylated [70,79] , and oxidatively dechlorinated [65,70]. It has been proposed that the metabolism of this compound may also involve arene oxide formation [65] , and chronic exposure to potential carcinogenic activity of resulting arene oxides [86] may result from the metabolism of this and similar compounds [75].
30 775331
GENP 006930
WATER PCB-SD0000056691
mgf-orical Reports
Smyth [119], in a paper read October 28, 1930, presented the results
of his studies with biphenyl, 2- and 4-chlorobiphenyl, and two unidentified
polychlorobiphenyl mixtures. He reported the oral minimum lethal doses for
rabbits and guinea pigs as 4+, 2.5, 3.5, 4+, and 4+ g/kg, respectively.
Health problems associated with the manufacture of PCBs were the
subject of a report by Jones and Alden [120] in 1936. The case history was
presented of a man whose employment, from April 1930 to the end of 1933,
involved the distillation of chlorobiphenyl. In May 1933 he developed
chloracne, a specific type of acne known to be caused by some chlorinated
hydrocarbon compounds [121,122]. Jones and Alden [120] stated that the
manufacturing process was not enclosed, that a different source of benzene
(a starting ingredient) had been used from- the summer of 1932 through
October 1933, and that from March to October 1933, the dielectric qualities
of the PCBs produced had been substandard. Of 24 men working in the
manufacturing process during the period beginning in the summer of 1932, 23
developed chloracne. The first indication of chloracne in the workers
appeared in January 1933. Following another change in the source of
benzene, enclosure of the distillation apparatus and installation of
ventilation fans, a gradual improvement in the acneiform eruptions was
noted.
'
In 1936, Schwartz [123] reported digestive disturbances, burning of
the eyes, and impotence in men working with chlorobiphenyls. He also noted
that nonachlorobiphenyl was used as an insulator for automobile electric
wires, in capacitors, and as a delusterer of rayon.
GENP 006931
31
775332
WATER PCB-SD0000056692
An early use of PCBs was for incorporation along with chloronaphthalenes into synthetic waxes [124-128], These waxes contained 10-20% PCBs [124-126] and were used to insulate electrical wire and cable. There were several reports that chloracne [125-128] developed in workers involved in the manufacture and use of these waxes, which were associated with at least one fatality in 1936 [125,127].
The fatal case was described by Drinker et al [125] in 1937. The patient, who had been exposed to low concentrations of tetra- and pentachloronaphthalenes (90%) and chlorinated' biphenyls (10%) developed chloracne, followed by jaundice. He was hospitalized with abdominal pain and distention. At autopsy, cirrhosis of the liver with superimposed acute yellow atrophy was found. Two other fatal cases were described where the exposures had been to mixtures of penta- and hexachloronaphthalenes [125] . According to the authors, no similar cases had been reported in the literature. As a result of these fatalities, estimates of the airborne concentrations of chlorinated hydrocarbons in 30 different factories were made and animal experiments were performed to study the effects of exposure at such concentrations.
Rats were exposed 16 hours/day, 6 days/week to trichloronaphthalenes at 1.31 mg/cu m, to a mixture of penta- and hexachloronaphthalenes at 1.16 mg/cu m, to a mixture of penta- and hexachloronaphthalenes (90%) and chlorinated biphenyls (10%) at 1.37. mg/cu m, and to a chlorinated biphenyl mixture containing 64% chlorine at 0.57 mg/cu m. The authors [125] stated that higher concentrations had frequently been found in the factories, and that except for trichloronaphthalenes, they did not consider that it would be safe to expose workers to any of the mixtures at the concentrations
32 775333
GENP 006932
WATER PCB-SD0000056693
studied [125], Further details of the animal experiment were reported by Bennett et al [129] in 1938. These investigators [129] found morphologic changes in the livers of two groups of rats exposed at the 0.57-mg/cu m concentration and also at 0.93 mg/cu m for 8 hours/day. These animal experiments reported by Drinker et al [125] and by Bennett et al [129] have continued to be erroneously cited [130,131] even though Drinker [132] reported in 1939 that the "chlorinated biphenyl" was actually a mixture of chlorinated biphenyls and chlorinated terphenyls. Drinker [132] stated that a followup inhalation experiment with chlorinated biphenyls containing 68% chlorine showed them to be of low toxicity and he recommended permissible limits for workroom air of 0.5 mg/cu m for mixtures of chlorinated biphenyls and terphenyls and 10 mg/cu m for chlorinated biphenyls.
The first indication in the literature that PCBs might be embryotoxic or have teratogenic effects was the report by McLaughlin et al [133] in 1963, 5 years prior to the recognition of PCBs as an environmental pollutant. The authors evaluated the toxicity of Aroclor 1242 by injecting it into the yolk sac of fertilized eggs prior to incubation, and then observing the effects on embryonic development. None of the eggs hatched after injection with 25 mg of PCBs/egg; with injection of 10 mg/egg, one chick hatched* out of 20 injected eggs, but it died 2 days later. Some of the embryos examined showed beak deformities, edema, and retarded growth.
Effects on Humans (a) Effects from General Environmental Contamination In the United States, PCBs are present in ambient air [26,37 ,38] ,
' 33
GENP 0069 3 3
7754
WATER PCB-SD0000056694
water [26,37], and in many foods [39,45,46], A common dietary intake of
10-20 ng/day has been estimated for teenage males in the US [46], PCBs
frequently have been found in various tissues and body fluids of the US population, eg, at ppm concentrations in adipose tissue [7,36,134-136], ppb concentrations in blood [137,138,140,141], and in milk [143,144] at ppm or ppb concentrations in the milk fat or whole milk, respectively.
The Environmental Protection Agency's Human Monitoring Survey has analyzed human adipose tissue samples collected since late 1968 for PCB content [134]. According to this 1972 report, 637 samples had been analyzed, and 198 of these contained more than 1 ppm of PCBs. Positive findings were made in tissues from each of the 18 participating states.
A detailed analysis of two samples collected in the Human Monitoring Survey was made by gas-liquid chromatography (GLC) and mass spectrometry (MS) and reported by Biros et al [135] in 1970. The samples contained at least 14 isomers ranging from penta- to decachlorobiphenyls. Price and Welch [36] stated that of more than 4,000 human adipose tissue samples examined by the Michigan State Department of Health Pesticides, none had chromatograms that exactly matched those of standard Aroclor solutions. Their data show relative accumulation in adipose tissue of the more highly chlorinated compounds, and relative dilution or absence of the less highly chlorinated compounds originally present in Aroclors 1254 and 1260. They [36] described the analyses of tissue samples at autopsy of a 77-year-old man in which PCB concentrations of 100-250 ppm (fat basis) were found The highest PCB concentration was in the liver. The authors [36] found about 55% of adipose tissue samples in the general population contained PCBs at <1,0 ppm, about 36% at 1-2 ppm, and the remainder at more than 2 ppm.
GENP 006934
WATER PCB-SD0000056695
During July 1972 through June 1974, 2,324 fat samples were analyzed by the Human Monitoring Survey, 1,277 in the first year and 1,047 in the second [136] . In the 2 years, respectively, PCBs were not detected in 24.5 and 9.1%, were present at <1 ppm in 40.2 and 50.6%, were present at >2 ppm in 5.5 and 4.9%, and were present at 1-2 ppm in the remainder of the samples. Penta-, hexa-, and heptachlorobiphenyl were the PCBs most frequently present.
A complete analysis of PCB compounds in a composite sample of adipose tissues from patients at the University Hospital in. Lund, Sweden, was reported by Jensen and Sundstrom [7] in 1974. Forty-five compounds, accounting for the total PCB content of the adipose tissues, were found and identified by comparison with known PCB isomers. The biphenyl compounds included three tetrachloro isomers, many penta-, hexa-, hepta-, octa-, and nonachloro isomers, and decachlorcbiphenyl. By comparison with Clophens A50 and A60, which had compositions similar to Aroclors 1254 and 1260, respectively, the authors [7] found the relative concentration of several compounds with chlorine substitution in the 4,4' positions of the biphenyl ring to have occurred, as did many compounds without vicinal, unsubstituted positions. Most of the compounds which underwent relative dilution to the greatest extant had either vicinal, unsubstituted 3,4-positions or two pairs of vicinal, unsubstituted positions.
Blood sera of 616 residents of urban and rural areas of South Carolina were analyzed for PCBs and the results were presented by Finklea et al [137] in 1972. Analysis was accomplished by GLC with a Ni-63 electron capture detector after basic dehydrochlorination. The amounts of PCBs present were estimated by integration of five peak areas associated
f.
k
r
GENP 006935
35
775336
1 WATER PCB-SD0000056696
with Aroclors 1254 and 1260, PCBs were not present in samples from all individuals in quantities measurable by the technique used (Table III-3) . Analysis of the data indicated that measurable serum PCB concentrations were not related to the age (<5 to >60 years) or sex (305 females, 311 males) of the donor, but that the concentrations associated with race and residence (Table III-3) were statistically different.
TABLE III-3
PCB CONCENTRATIONS IN BLOOD SERUM BY RACE AND RESIDENCE
Race and Residence
No. in Sample
PCBs Measureable In No. %
PCB Concentrations
Ave*
Max
ppb ppb
Rural black Urban black Rural white Urban white
107 151 192 166
5 57 119 89
*Average of meaaureable concentrations
Adapted from reference 137
4.67 37.75 61.98 53.61
9.45 5.22 5.12 4.38
20.6 29.0 16.6 22.0
Maternal and cord blood samples collected in Tokyo, Japan from December 1973 through February 1974 were reported in 1975 by Akiyama et al [138] to contain PCBs at mean concentrations of 2,8 and 1.1 ppb, respectively (on a whole blood basis). The maximum concentrations found were 7.6 ppb in maternal blood and 3.3 ppb in cord blood. Quantitatively, significant correlations of PCB concentrations in 21 pairs of maternal and cord blood samples were not found. Qualitatively, pairs of maternal and cord bloods had identical PCB patterns resembling those of Kanechlors 500
36 775337
GEJV] vuo936
WATER PCB-SD0000056697
and 600. The data suggested nonselective In utero transfer of PCB
compounds from mother to fetus. Concentrations of PCBs in human embryonic
and fetal tissues were reported by Shiota et al [139] in 1973 to not exceed
those found in postnatal' individuals who died accidentally.
The
concentrations, found in 19 embryos 5-8 weeks old, were reported as <2 ppb.
The concentrations found in 5 second trimester and 2 third trimester
fetuses are presented in Table III-4, expressed on the bases of both whole
tissue and on the fat content of the tissue.
TABLE III-4 CONCENTRATIONS (ppb) OF PCBs IN TISSUES OF HUMAN FETUSES
Age of Placental Basis Contents
Cerebrum
Tissue Analyzed
Liver
Kidney
Skin
2nd trimester
Whole Fat
3rd trimester
Whole Fat
*0ne sample
Adapted from reference 139
2-23 150-60
2* 270*
2-33 230-800
6-20
17-83
60-1,900 550-1,300
25-90
6-10
1,000-1,300 420-470
48-769' 880-1,400
PCB concentrations in the venous blood of nine patients hospitalized with severe wasting diseases were reported by Hesselberg and Scherr [ 140] in 1974. The investigators were concerned with the release of stored organo-halide pesticides and PCBs during mobilization of body fat. They were unable to detect any PCBs in the blood of 15 apparently healthy
GENP 006937
WATER PCB-SD0000056698
control subjects. PCB concentrations found in the patients' blood (uncorrected for efficiency of recovery) ranged from 10 to 100 ppb. Information was not presented on the patients' occupations etc prior to their having become ill.
PCB concentrations in blood plasma and in adipose tissue samples obtained from 28 people during routine abdominal sections had a correlation coefficient of 0.74 according to Inoue et al [141]. The average concentration of PCBs was 6.13.52 ppb in blood plasma, and in the adipose tissue (fat basis) it was 2.6+1.9 ppm. These investigators [141] also evaluated the effect of emaciation on PCB concentrations in blood plasma of these and other patients; they found an average of 8.4+4.26 ppb in 19 emaciated patients and 4.72.17 ppb in 30 unemaciated patients.
Hair samples collected from a college barber shop were reported by Matthews et al [102] in 1976 to contain PCBs at 0.34-0.76 ppm. The samples were composites from five or more individuals collected on two occasions, 4 months apart. Hair was collected from the barber shop aprons, and care was taken to avoid possible contamination. Five commercial preparations of hair sprays, shampoos, and hair clipper lubricating oil were negative for PCBs. Blood samples were not collected for comparison.
PCBs were reported in 1966 to have been found in hair samples from three members of a Swedish family [142], but no concentration data were given. It was speculated that one of the family members, a 5-year-old girl, had acquired PCBs from her mother's milk.
A correlation was found between the quantities and compositions of PCBs in samples of adipose tissue collected from four women during Caesarean deliveries and in milk samples collected 3-5 days later [143] .
38
' 775339
GENP 006938
WATER PCB-SD0000056699
There were differences in chromatographic patterns between individuals, but for each individual the chromatographic patterns for the adipose tissue and che milk were qualitatively the same. PCBs in all samples contained principally 4-8 chlorine substitutions. Although the basis (fat or whole milk) for expressing the concentration of PCBs in the milk was not stated, comparisons with PCB concentrations found in adipose tissue and milk by other investigators indicate that the whole milk basis was used [136,144] (EP Savage, written communication, February 1977). Concentration data are summarized in Table III-5.
TABLE III-5 PCBS IN MILK AND ADIPOSE TISSUE OF FOUR WOMEN
Subject
PCB Concentrations, ppm
Adipose Tissue
Milk
a b c d
Adapted from reference 143
. 0.62 0.75 1.6 3.1
0.008 0.015 0.032 0.036
Concentrations of PCBs measured in milk samples from 39 women living in two small cities in Colorado were presented by Savage et al [144] in 1973. Two samples contained PCBs at concentrations of 0.05 and 0.1 ppm. Six other samples contained PCBs at 0.04 pvm, the lower limit of detection for the analytical method, or less. The time postpartum at which the samples were collected and the basis (fat or whole milk) for expressing the concentrations were not mentioned. (Comparison with data in the following
39
GENP 006939
775340
WATER PCB-SD0000056700
paragraph suggests that the whole milk basis was used.) Results of analyses of 384 human milk samples from 40 states for PC3s
were presented in a written communication by EP Savage in February 1977. All positive samples that contained PCBs at less than 50 ppb on a whole milk basis were recorded as a "trace." Samples with 50 ppb or more of PCBs were reported as ppm in milk fat on the basis of 2.8% milk fat. Only five samples were not positive for PCBs, and 112 samples from 27 states contained measurable amounts (up to 12.6 ppm on a fat basis). Of the total number of samples, 141 were analyzed during December 1976 and January 1977. The time postpartum when the samples were collected was not stated.
While no adverse effects have been associated with PCBs at the concentrations found in adipose tissue, blood, or milk of individuals whose only known exposures were from general environmental contamination [7,36,102,136-144], knowledge of these concentrations is important to the evaluation of reports on occupational exposures. That is, the data provide a basis for evaluating body burdens of PCBs added by occupational exposure and indicate that workers may have substantial body burdens before the added insult of occupational exposure.
(b) Effects from Consuming PCB Contaminated Rice Bran Oil An episode of poisoning associated with PCB ingestion occurred in Japan in 1968, and was the subject of a special issue of the journal Fukuoka Acta Medica in June 1969 [145-159]. These reports dealt primarily with the situation in Fukuoka prefecture where 325 poisoning cases had been identified through January 20, 1969. The episode resulted from consumption of a particular brand of rice bran oil [160] and ultimately involved persons in 22 prefectures [161] . About equal numbers of cases
40 775341
GENP 006940
WATER PCB-SD0000056701
(approximately 150 each) were registered in Fukuoka and Nagasaki prefectures as of' September 1973 [161], ln the prefectures of Hiroshima, Kochi, and Yamaguchi, there were 80, 45, and 40 cases, respectively, at that time. In each of the other 17 prefectures there were 1-25 registered cases. The total number of cases registered by March 1970 was 1,015; by September 1973, the number had increased to 1,200, and by May 1975 to 1,291 [161.162]. The disease became known as "Yusho," or rice oil disease [145.163], The outstanding signs of the poisoning were acneiform eruptions and eye discharges (a peculiar secretion from the meibomian glands) [146], Chloracne was suspected [164]. Hyperpigmentation of the skin, nails, and mucous membranes, swelling of the upper eyelids, and hyperemia of the conjunctivae were other common signs [146,165],
Studies of the rice oils consumed by the patients indicated that the oil associated with Yusho was produced mainly during February 1968 [147,148], The source of the contamination was determined to be a heat exchange unit containing PCBs that leaked through tiny holes when rice bran oil was heated at low pressure to remove odorous constituents [163,165], 3v intensive chemical analyses, including infrared spectrophotometry and GLC, the major contaminant in the rice bran oil was found to be Kanechlor 400 [1-7]. PCB concentrations in the oil varied, depending on the date of production or shipment. The highest concentration of PCBs, based on the chlorine content of the oil, was about 3,000 ppm which was found in canned oil shipped on February 5. GLC data were not quantitated. In oils shipped thereafter, PCB concentrations decreased rapidly, and only traces were found in oils produced after February 19, 1968 [147,148], Minor contaminants in the rice oil included polychlorinated dibenzofurans at
41 775342
WATER PCB-SD0000056702
about 1/200 of the PCS concentration [20,160], traces of chlorinated naphthalenes, and bromine at about 17. of the chlorine content [147]. Recent analyses of some of the oil samples indicate that there may have been other chlorinated organic contaminants (F Cordle, written communication, November 1976).
In one study [148], the contaminated rice bran oil was found to have been used largely for frying food (which may have altered the constituents). The oil was consumed for various periods during the springthrough October 1968 [148]; the first reported clinical examination of a Yusho patient had occurred on June 7, 1968 [163], Studies through January 1969 of patients in Fukuoka prefecture indicated that onsets of Yusho began as early as February and as late as December 1968, and first involved the eyes [146], Onset occurred in most patients in June, July, and August [146].
Some attempts were made to estimate the amounts of rice oil and PCBs consumed by the patients [166,167], Maximum consumption of oil was estimated at 4.4 liters [166], Isono and Fujiwara [167] estimated that two Yusho cases may have resulted from the ingestion of PCBs at a daily rate of 67 jig/kg body weight for 3 months. For 146 Yusho patients who lived in homes known to have used oil shipped on February 5-6, the estimated average total oil consumption was 800 ml, a volume that contained an estimated 2 g of PCBs [166], It was estimated that the maximum volume of oil consumed by an individual was 2.7 liters. Of 21 patients who had consumed more than 1,400 ml (3-4 g of PCBs), 18 were considered to have had major signs of Yusho. Among 80 patients estimated to have consumed leas than 720 ml of the oil, 31 were thought to have had major signs of Yusho. From the same
42 '
GENP 006942
WATER PCB-SD0000056703
data, the minimum PCB ingestion among the 146 patients was estimated at 0.5 g [165]. Estimates of the amount of contaminated oil consumed by 13 pregnant women during the ingestion period ranged from 300 to 2,600 mg [167], but estimates of their PCB consumption were not made. Of the 13 babies born to these women, 8 had jaundice, 3 had marked dermal chromopexy, and 9 had excess secretion of tears [167],
Several studies of PCBs in the tissues and body fluids of Yusho patients were made at various intervals after ingestion of the contaminated oil [146,147], The samples taken closest to the time of ingestion were collected in October and November 1968 [146,147], Samples from discharges of the acneiform eruptions of two patients contained PCBs at 32 and 45 ppm, and samples of subcutaneous fat from the face and abdomen of an 18-year-old man contained PCBs at about 75 and 13 ppm, respectively. PCBs with GLC patterns similar to those of the contaminated oil were found in these samples as well as in placental and fetal tissues [147], Preserved tissues from a baby that had been stillborn in October 1968 were later analyzed and PCB concentrations of 1.8, 1,2, and 0.1 ppm in fat were found in the liver, skin, and fat, respectively [168], The baby's mother had been classified as a severe case of Yusho with onset about mid-June, but the amount of oil consumed, the period of pregnancy during which it was consumed, and the body burden of the mother were not reported [149]. PCBs were found in all sputum samples from 13 patients collected between December 1969 and May 1970 [ 169,170] . PCB concentrations were highest in December and detection was less common by May.
Other data on concentrations of PCBs were obtained from body fat and other tissues taken from five Yusho patients at autopsy [168,171], The
GENP 006943
43
775344
WATER PCB-SD0000056704
.x
dates of death were between July 1969 and May 1972, Cause of death was heart failure in four cases and a ruptured liver in another case [171]. Estimates of contaminated oil consumed by two of the dead patients were about 0.3 g and 1.6 g, respectively [171], One PCB, probably a hexa- or heptachlorobiphenyl from the contaminated oil, was especially concentrated in the tissues. The peaks associated with tetrachlorobiphenyls were very low by comparison, suggesting that total PCBs in the body had been substantially decreased within a year after the end of exposure. The mesenteric fat contained PCBs at 0.9-15.1 ppm, and the liver contained 1.3 10.4 ppm in its fat. PCB concentrations in fattv tissues obtained during 11 control autopsies averaged 2.6 ppm. Of the organs examined (liver, heart, kidney, brain, and skin), the liver and heart usually contained the highest concentrations of PCBs [168,171]. '
In an additional case, the subcutaneous fat obtained on autopsy of a woman who died in * September 1972 (about 2 years after consuming contaminated oil) contained PCBs at 2.9 ppm [168].
Polychlorinated dibenzofurans (PCDFs), mainly penta- and hexachloro compounds, were found in tissues obtained on autopsy of two Yusho patients who died in 1969 and of one who died in 1972 [160], No chlorinated dibenzofurans were found in tissues obtained on autopsy of two controls, although PCB concentrations of about 1-1.5 ppm were found in adipose tissue and liver fat. The findings from the Yusho patients are summarized in Table III-6.
i
775345
44
GENP 006944
WATER PCB-SD0000056705
TABLE III-6 PCBs AND PCDFs (ppm) IN FAT FROM THREE YUSHO PATIENTS AT AUTOPSY
Year of Death
PCBs
Adipose
Liver
PCDFs
Adipose
Liver
1969
3.4
1969
8.5
1972
2.1
Adapted from reference 160
4.7 5.6 3.5
0.03 0.04 0.01
2.3 1.1 0.3
The ratio of PCBs to PCDFs in the rice bran oil was about 200, as in the adipose tissues obtained at autopsy. However, in the liver, ratios . of 2, 5, and 12 indicate that considerable concentration of PCDFs had occurred.
Information on PCBs [146 ,147,168,171;] and PCDFs [160] in tissues indicates some shifts in concentrations during the 3 years after ingestion of the contaminated oil was discontinued. Masuda et al [168] reported that a year after ingestion stopped, the concentrations of tetrachlorobiphenyl components had decreased and were near those found in persons who had not ingested the contaminated oil. The more highly chlorinated PCB compounds were still retained in the fatty tissue 4 years after ingestion had stopped [168] .
Blood from Yusho patients was first examined for PCBs 5 years after ingestion of the contaminated oil ceased. Three distinct GLC patterns were found among blood samples from 49 patients [ 172-175]. Two patterns (A and B) were peculiar to the Yusho patients, and the third pattern (C) was
GENP 006945
45
775346
WATER PCB-SD0000056706
similar to Chat of controls. Patterns A and B were characterized by peaks corresponding to chose of certain penta- and hexachlorobiphenyl compounds that were present in the contaminated rice bran oil. Patterns A and B differed, however, as to the relative amounts of these compounds [172,173]. These patterns became diagnostic for Yusho [161]. The average concentrations of PCBs in the blood serum were 9, 4, and 2 ppb for patients with patterns A, B, and C, respectively, and 3 ppb for 27 control subjects [173]. The maximum blood serum PCB concentration found among 72 Yusho patients examined between April 1973 and March 1974 was 26 ppb [174], Of these patients, 43 had pattern A, 26 had pattern B, and 3 had pattern C.
Similar patterns were reported in 1975 by Abe et al [176] in a 1974 study of 18 female Yusho patients and their 30 children. Concentrations of PCBs in blood samples from mothers ranged from 3 to 33 ppb during 1974; PCBs in samples from their children ranged from 1 to 20 ppb, and in samples from 14 control children, from 1 to 8 ppb. PCB concentrations tended to be higher in the blood samples from children nursed by Yusho mothers. A sample of milk from a Yusho mother was reported in 1974 to contain PCBs with a GLC pattern similar to those in samples of fatty tissue from other Yusho patients [168]. Concentrations of PCBs in the mother's milk were 0.06 ppm on postpartum days 0-2, 0.04 ppm on days 3 and 4, and 0.03 ppm on day 5. The respective concentrations in the milk fat were 4.5, 3.0, and 2.6 ppm.
In addition to the skin and eye conditions manifested by most people who consumed the contaminated rice bran oil [146,151-153,162], there was pigmentation of the nails [146] and of the oral mucosa [154]. A substantial array of clinical and laboratory findings were published on
46 775347
GENP 006946
WATER PCB-SD0000056707
patients with Yusho [150,152,155,156,177-180], including slight increases
in activity of serum alkaline phosphatase, reduced serum iron
concentrations [155], changes in the microanatomy of liver cells that were
considered indicative of microsomal enzyme stimulation [156], symptomatic
and functional changes indicative of neuropathy [150,177] , respiratory
involvement [170,178], a decreased concentration of bilirubin in the serum
-[179], and, in many patients, an elevation of the concentration of
triglycerides in the serum [155,157,158,175,179-181].
Babies born to women with Yusho, both during and after the period of
ingestion of the contaminated rice bran oil, were the subject of several
investigations [149,159,176,182,183]. Babies of mothers who had ingested
the contaminated oil became known as "black" or "cola" babies because of
the abnormal skin pigmentation that tended to persist for several months
after their birth [176,182,183]. Infants born up to 5 years after their
mothers' last ingestion of contaminated rice oil were still affected to
some extent [182] . In one study of four babies, other clinical and
anatomical abnormalities (retarded intrauterine growth in three, edematous
face and exophthalmic eyes in three, dentition in two, calcification on
skull and wide, open sagital suture of skull in three) were seen at birth
[183]. These were not permanent, and postnatal body and mental development
appeared normal in these and other Yusho children [160,176,183]. In at
least one case, an investigator concluded that a baby had developed Yusho
from nursing [182] .
_
The period of ingestion of contaminated rice bran oil was only a few
months, but the effects have persisted for several years
[160,161,174,175,179,180,184,185]. The skin lesions and hypersecretion
47
GENP 006947
775348
WATER PCB-SD0000056708
from meibomian glands remained unchanged for long periods in many patients [174,184,185]; their magnitudes in 1974 appeared to be related to blood PCB concentrations [174], In addition, complaints of generalized fatigue, and symptoms referable to the peripheral nervous system and to the respiratory system became more prominent. In 1974 these complaints and symptoms were established as part of the diagnostic criteria for Yusho [161]. These
additional symptoms were not related to the PCB concentrations in the blood [174].
Elevated serum triglyceride concentrations were found to be related to the concentration of PCBs in the blood serum [175], and inversely related to the bilirubin concentrations in the serum [179]. The average serum triglyceride concentrations measured annually in 14 Yusho males from
'.
1969 through 1974 ranged from 159 mg/100 ml in 1969, to 174 mg/100 ml in 1972, to 160 mg/100 ml in 1974 without any significant changes from year to year. In 29 Yusho females, the concentrations initially (1964) averaged 153-161 mg/100 ml, but decreased in 1973 and 1974 to 129 and 111 mg/100 ml, respectively [180].
The Yusho population of about 1,300 persons has been followed closely and records indicate that as of May 1975, 29 of them had died [162], Deaths have been due to a variety of causes such as accidents, suicides, cardiac problems, and cancers. Malignant neoplasms were found in at least nine cases [161], from which Kuratsune et al [160] concluded that there was a suggestion of excess deaths but that no more could be said because information essential for analysis was not available.
The relevance of the Yusho episode to occupational PCB exposure is compromised because: (1) the oil was ingested; and (2) it contained large
48 . 775349
:
;
j
! ; |
j_ \
t
[
i
. f \
i
j
j
GENP 006948
WATER PCB-SD0000056709
concentrations of dibenzofurans compared with those in the PCBs to which workers generally have been exposed in their occupations. Its relevance is further compromised because the effects observed from daily ingestion of 1 15 tng of PCBs [165,167] were peculiar and excessive compared to those observed in workers exposed by inhalation to PCBs at 1-5 mg/cu a [120,125], notwithstanding that the amounts absorbed may have been similar.
Nevertheless, information obtained from the Yusho episode is relevant to the study of PCB toxicology and occupational exposure. The information establishes that PCBs can be transmitted from mother to fetus, and, in the milk, from mother to child. It also establishes that some PCB compounds are eliminated from the body relatively rapidly, and that others may require years for elimination.
(c) Occupational Exposures Chloracne was among the ear]iest reported effects associated with worker exposure to PCBs [125-128] . It was not clear in some early reports that PCBs were contributing to the chloracne because PCBs usually constituted 10-20% of mixtures containing 80-90% chloronaphthalenes, a previously known cause of chloracne [ 121,122]. An early report that associated chloracne with PCBs in the absence of chloronaphthalenes was that of Jones and Alden [120] in 1936. The manufacturing process was largely an open one and the workers were also exposed to benzene, biphenyl, and other compounds incidental to PCB manufacture. Over the years, cases of chloracne associated with occupational exposure to PCBs have continued to appear [186-196], Other effects associated with PCBs in early reports included digestive disturbances, eye irritation, liver injury, and impotence
GENP 006949
49
7753S0
WATER PCB-SD0000056710
[123,125], Elkins [130] reported in 1950 that the average concentrations
of PCBs in the workroom air of several plants in Massachusetts ranged from
0.1 to 5,8 mg/cu m. Maximum concentrations ranged from 0.2 to 10,5 mg/cu
m. No evidence of immediate toxic effects was observed except at PCB
concentrations approaching 10 mg/cu m, which the workers found to be
unbearably irritating.
Three cases of severe chloracne were described by Puccinelli [186] in
1954. The affected employees worked in a factory that produced capacitors
impregnated with Aroclor 1254. The workroom was 24 x 9 x 5 meters.
Capacitors were heated to about 100 C in a 3-cu m autoclave to remove
moisture, and then impregnated with the Aroclor while in the autoclave.
The temperature in the autoclave was reduced about 12 hours later. When
the autoclave was opened, the temperature of the Aroclor was 70-80 C. The
capacitors were removed and carried to another location for finishing.
Originally, one autoclave was used, but eventually eight were in operation,
and PCB emissions to the workroom air occurred almost continuously.
Concentrations of PCBs in 500-liter samples of air were found to vary from
5.2 mg/cu m in the center of the room, to 6.4 mg/cu m around the finishing
operation, to 6.8 mg/cu m near the autoclave during removal of the
capacitors. The three chloracne cases were in men, 18-24 years of age.
They had worked in the factory for 2-4 years, and developed the first signs
of chloracne 4-8 months after their exposures began. Other than chloracne,
the men appeared healthy, and all findings, including liver function tests
were reported as normal.
'
Eight other cases of chloracne associated with PCB exposure during
the manufacture of radio capacitors were described by Hofmann and Meneghini
50 775351
GENP 006950
WATER PCB-SD0000056711
C ]_ 5 7 ] in 1962. In the process, PC3 vapors were generated by heat. The
cases included one man and seven women, 20-37 years of age, who were
exposed to PC3s 2.5-4 months before onset of signs of chloracne. The face
was involved in six cases; other involved areas varied, but included the
arms, neck, upper torso, pubes, buttocks, and thighs. The case of a 21-
year-old woman was described in detail. The first signs of chloracne
,appeared on her face 4 months after she began work, and she was observed by
the authors [187] 4 months later. On the face, a dirty brown coloring
appeared. A hyperpigmented spot with shaded areas was present on the
forehead. Subsequently, her buttocks and pubes became involved. Exposure
concentrations were not mentioned.
Severe chloracne was described by Birmingham [188] in 1964 in 13 of
15 workers exposed to an Aroclor which was a mixture of bi- and terphenyls
(65% chlorine content). An enamel containing the Aroclor was painted onto
glass and then baked in an oven. Faulty ventilation caused contamination
by chlorinated hydrocarbon vapors. Exposure concentrations and duration of
exposure were not given.
An additional case history published in 1969 involved a 43-year-old
man exposed to PCBs in an electrical component factory [189], He developed
chloracne on the forehead, face, arms, and thighs within 3 months after
beginning work handling racks of electrical parts that had been dipped in
hot PC3s. Exposure concentrations and actual durations of exposure were
net stated, but it was reported that the man had put his hands in the
mixture without skin protection for a long time, and that his clothes often
became impregnated with the PC3s. On examination 8 months after transfer
to another job in the same room, papules, comedones, and pustules were
GENP 006951
. . ..
..
51 ......
. 775352
WATER PCB-SD0000056712
found on his forehead, scalp, face, and arms. Although the man had been
removed from direct exposure to PCBs, their odor was present in the man's
new work area. It was reported that this was the first case of chloracne
in the plant, where more than 100 workers had been engaged in the process
for more than 20 years,
A company that used PCBs at two manufacturing facilities provided
testimony on employee health in 1975 (In the Matter of General Electric
Company, File No. 2833, New York State Department of Environmental
Conservation). Examination of records submitted as testimony Indicated
that exposures were to an askarel [25] containing, by weight, about 60% of
Aroclor 1254, 40% trichlorobenzene, and 0.0115-0.135% diepoxlde scavengers.
From the records submitted, it was not possible to determine the precise
numbers of male and female workers. The exact occupations of the workers
could not be determined either but a substantial number of "crimpers" was
Indicated.
The records showed .that employees had reported to the dispensary
complaining of skin rashes and dermatitis on 49 occasions during the
previous 15 years. Only the fingers and hands were involved in 21
complaints, only the arms and hands in 5, and only the face and legs in 1.
In 7 other complaints the face, neck, and legs were mentioned in 4, 2, and
1 cases, respectively, in addition to the upper extremities. Associated
with the complaints of skin rashes and dermatitis were some complaints of
itching of the face (2), neck (1), eyes (1), arms (2), and hands (1). A
generalized skin rash was the basis of 14 additional complaints. One
worker developed the generalized rash on exposed parts of his body after
only 2 days of working with the askarel. 52
^75353
GENP 006952
i j
)
!
(
i
i
i
i!
WATER PCB-SD0000056713
The company physicians attributed the rashes to allergic or contact
dermatitis caused, by exposure to the askarel. Treatment included the use
of creams, and temporary or permanent removal from exposure. Of the 49
complaints, 22 were second episodes, and in these cases the workers were
removed permanently from exposure to askarels. One female employee who had
dermatitis of the fingers was removed from exposure for 12 days. Within 2
- days of reexposure she again reacted to the askarel and was permanently
removed from such work.
.
Over the same 15 years, other kinds of complaints were made by the
workers on 16 occasions. These complaints included burning sensations of
the eyes (7), nose (1), and face (1); dry throat (1); asthmatic bronchitis
(3); nausea (1); dizziness (1); and aggravation of acne (1). In- most of
these cases, the company physicians recommended permanent removal from
exposure.
The health status of eight laboratory workers who routinely analyzed
dielectric fluids containing PCBs was reported by Levy et al [197] in 1977.
The men were 25-49 years of age and had been employed 2,5-18 years.
Breathing zone, point source, and general work area air samples wer.e
collected on magnesium silicate at 50 ml/minute over the workday on three
occasions. The breathing zone samples contained PCBs at 0.014-0.073 mg/cu
m. Samples taken near an oven contained 0.042-0.264 mg/cu m, and general
room area samples contained PCBs at 0,013-0.15 mg/cu m. The blood PCB
concentrations in the workers were 36-286 ppb. The most common complaint
of the workers (6 of 8) was dry or sore throat. Other complaints were skin
rash (3 of 8) , gastrointestinal disturbances (3 of 8), eye irritation and
headache (each, 2 of 8) . Findings on examination of the eight workers were
53
GENP 006953
7.753S4
WATER PCB-SD0000056714
akin rash (1), nasal irritation (2), rales (1), and elevated blood pressure
(A). No liver, spleen or neurologic abnormalities were found by physical
examination.
There were no cases of chloracne. Serum alkaline
phosphatase, SGOT, SGPT, and total bilirubin, measured in seven subjects,
were all within normal limits. In addition, medical records of AO other
exposed employees were examined, revealing two cases of slightly increased
SGOT, two elevated serum triglycerides, and one case each of increased
serum alkaline phosphatase (SAP) activity, total serum bilirubin, and serum
uric acid.
Epidemiologic Studies An outbreak of dermatitis among workers in a Connnecticut chemical
plant was described in 195A by Meigs et al [190], PCBs had been substituted for molten salt in a heat exchange unit without modification of the system. There were alight, but obvious, vapor leaks under certain conditions, and the concentration of PCBs in the workers' breathing zones was determined to be 0.1 mg/cu m. No employee worked regularly at points of leakage, and the operations, as described, continued for 19 months.
Mild to moderate chloracne on the face, forehead, and ears developed in 7 of 1A exposed workers; the mastoid region of one worker also was affected. The duration of exposure before the initial signs occurred ranged upward from 5 months and averaged 1A months. The average length of exposure was 11 months for those who did not develop chloracne, with one worker showing no signs after 19 months. Liver function tests were performed on the seven workers who had developed chloracne. Clinical tests included direct and total serum bilirubins, 2A- and A8-hour cephalin
5A 775355
GENP 006954
WATER PCB-SD0000056715
flocculations, thymol turbidity, and SAP activity. Findings were normal in six workers, and borderline increases in cephalin flocculation and thymol turbidity were found in the seventh worker with chloracne. Thirteen months later, the thymol turbidity test had improved, but cephalin flocculation had not changed. All cases of chloracne were stated to have cleared up after an unspecified treatment. Control of vapor emissions by welding all joints in the heat exchange unit prevented recurrence [190].
Exposures of workers to PCBs in six industrial plants were discussed by Hasegawa et al [191] in 1972. The concentrations of PCBs found are summarized in Table III-7.
TABLE III-7 RANGE OF PCB CONCENTRATIONS (yg/cu m) IN WORKROOM AIR
Factory
Function
No. Samples
A
PCB manufacture
6
B Capacitor manufacture 3
C
Biphenyl recovery
2
D Capacitor manufacture 2 E 1* 3
*1 sample **6,270 due to spillage
Adapted from reference 191
PCB Concentrations
Vapors
Particulates
26-163 120-350
13-15 350-540
95-965
19-37 20-125
4* 48-6,270** 73-650
ENP 006955
55
775356
WATER PCB-SD0000056716
PCBs were manufactured in one plant and uaed in manufacturing
capacitors in four plants (one had discontinued use of PCBs 1 month
earlier). Biphenyl, not chlorobiphenyls, was present in the sixth plant
[191], Air samples were collected in two fractions. A fraction associated
with particles >0.lji was collected on filter paper, and a fraction
containing vapors and particles <0.1y in diameter was collected in two
serially-connected midget impingers. containing n-hexane. Samples were
collected only from places where high concentrations of PCBs were expected
and not from the factory where PCB use had been discontinued.
The vapor concentration exceeded the particulate concentration in all
except the sample taken after spillage.
Particulate matter was
characterized by GLC as containing the same chlorobiphenyl composition as
the PCB product uaed in the plant, whereas the vaporized material contained
one less chlorine atom/molecule than the PCB used in the plant.
PCBs were measured in the blood of the employees of six plants,
including 99 exposed workers and 32 controls [191]. Concentrations of PCBs
in the blood sera of exposed workers averaged 370 ppb, whereas those of the
controls averaged 20 ppb. The workers exposed to PCBs in the plant that
had discontinued PCB use had serum PCB concentrations of 90 to 730 ppb
(average 460 ppb). Based on data from three of the plants, no relationship
was found between duration of exposure (from <1 to 20 years) and
concentration of PCBs in the blood [191].
Complaints of dermal ailments seemed to be unrelated to the blood PCB
concentrations and were considered to be due more to direct contact of the
skin with PCBs than to generalized intoxication. The principal dermal
findings included brown chromodermatosis of the dorsal Joints of the hands
56
WATER PCB-SD0000056717
anCj fingers and of the nail bed, and acneiform exanthema. The latter also involved the jaw, back, and theighs in several cases. The investigators [191] considered that there was a definite effect of PCBs on fat metabolism, as shown by decreases in the concentrations of total, free, and esterified cholesterols in the blood, and by trends in the same direction for neutral fats, total glycerides, phospholipids, and beta-lipoprotein in " the blood. There was evidence of mild disturbances of liver function manifested by increased SGOT, SGPT, and SAP activities and decreased activity of serum cholinesterase. These enzyme activity changes were not considered to be clinically significant.
Studies of 38 current and 80 former employees of a capacitor factory in which Kanechlor 500 had been used from 1954 to about 1960 and Kanechlor 300 had been used from about 1960 to 1972, with PCB use having been discontinued in April 1972, were reported by Hara et al in 1973 [192] and again in 1974 [193]. (Presumably, this factory was the one stated by Hasegawa et al [191] to have discontinued use of PCBs.) Current workers included 17 who were engaged in the capacitor immersion process; the remaining 21 workers were engaged in finishing and assembling operations. The study concentrated on the 17 immersion process workers. During exposure to PCBs in March 1972, the concentrations of PCBs in the whole blood of the immersion workers ranged from about 7 to 300 ppb, and were closely related to years of exposure. One year later, blood PCB concentrations had all decreased, but by varying amounts. For example, one of two workers who initially had PCB concentrations in their blood of about 180 ppb had a concentration of <10 ppb 1 year later, while the other one had a concentration >100 ppb. The average PCB blood concentration for the
57
775358
WATER PCB-SD0000056718
17 workers decreased to about 75% of the original value ,, Based on blood samples collected about 6 and 12 souths after use of PCBs was discontinued, the blood PCB half-lives for the l^ersiem workers were calculated. It was found that the greater the duration of exposure, the greater the PCB half life (1 year of exposure, 3 souths half-life; 10-15 years of exposure, 30 souths half-life). This indicated to the investigators that blood served as a PCB carrier, whereas fat served as a depot tissue [192].
While working with PCBa, many of the total group of employees had derma! cosplainta (blackheads, 45%; acnelfora eruptions, 37%; skin Irritations, 13%) [192]. A year after discontinuance of exposure to PCBs, these conditions had improved noticeably and only one or two blackheada resaalned. Ho correlation was apparent when concentrations of PCBs and triglycerides In the sera of a large number of workers were compared graphically. The workers were also studied about 18, 24, and 36 months after use of PCBs had been discontinued [ 193] ,, During this period, blood PCB concentrations decreased to about 10-20 ppb 1s all but two workers who had been exposed to PCBs for 9 and 15 years. The skin disturbances were reduced to vestigial workings on a few Individuals. Comparisons with the concentrations of triglycerides and PCBs in the sera of these workers indicated that the. proportion of workers with significant Increases in triglyceride - concentrations Increased as the concentrations of PCBs increased. Of nine workers with blood PCB concentrations >50 ppb, five had elevated triglyceride concentrations.
Examinations of 13 workers from an electrical capacitor manufacturing plant for clinical manifestations of PCB toxicity were reported by Kltaaszra et al [194] in 1973. Examinations were performed when the company
1
-4
3
s
58 775359
69S8
WATER PCB-SD0000056719
discontinued the use of PCBs in June 1972, and were performed twice subsequently at 3-month intervals. The average length of worker exposure to PCBs had been about 2.5 years. Immediately after discontinuance of PCB use, the average PCB concentration in the blood of workers was 820 ppb, ranging from 320 to 2,100 ppb [194], The mean concentration fell to 310 ppb after 3 months, and to 200 ppb after 6 months. From these observations, Kitamura et al [194] estimated the biological half-life of the PCBs in the blood immediately following the cessation of exposure to be about 90 days. No consistent correlation could .be found between the concentration of PCBs in the blood and the duration of exposure to PCBs. Nail, hair, and gum color and color of the mucous membranes of the oral cavity all were normal. Ten of the workers had varying degrees of skin disorders on different parts of their bodies. The skin disorders included seborrhea adiposa, acne vulgaris, and follicular papules on parts of the body where direct contact with the PCBs normally did not occur. The authors [194] concluded that PCBs probably had been an important factor in the etiology of the skin disorders and that results of blood tests, hepatic function tests, and urinalyses were normal. Serum triglycerides were not determined.
A study by Inoue et al [ 195] of the health of workers in family-owned silk-thread glossing factories in which PCBs were used was published in 1975. The study was initiated because PCB concentrations exceeding 100 ppb had been found in the blood of a 73-year-old man who had undergone surgery. His family operated a household thread-glossing factory. The family members and the hired helper were studied. Serum concentrations of PCBs resembling Kanechlor 500 ranged from 130 to 520 ppb. There was a close
GENP 006959
59
775360
WATER PCB-SD0000056720
correlation between the PCB concentration in the blood and the degree of
involvement in the glossing work. The head of the household had skin
lesions and comedones on the face, back, and ears and had blood PCB
concentrations of 190-210 ppb. The rest of the people had practically no
akin abnormalities, and other findings (not described) were, in general,
considered of minor significance. A study of PCB contamination of the
premises and the air of the same factory was reported by Fujiwara et al
[33]. At the time the samples were taken, use of PCBs had been
discontinued. However, PCBs were found in air at 0.25 mg/cu m, in floor
boards at 80-130 ppm, in the dirt under the machinery at 10-900 ppm, and in
the dust on steel frame beams at 110-180 ppm. The PCBs were similar to
those in Kanechlor 500.
.
Subsequent to the above study, Inoue et al [195] reported on the PCB
concentrations in samples of blood obtained from 54 other similarly
employed people. PCB'concentrations of over 100 ppb, 50-99 ppb, 10-50 ppb,
and 0-9 ppb were found in 2, 5, 19, and 28 persons, respectively.
Correlative comparisons with thevarious functions
performed in the
factories showed that those workers who had direct contact with the
glossing machines, those who maintained and repaired the machines, and
those who had over 20 years of work experience had the highest
concentrations of PCBs in their blood. Skin abnormalities and other
findings in these 54 persons were described as relatively mild. One of the
persons studied, a woman in her 10th month of pregnancy, had a serum PCB
concentration of 24 ppb. Following birth, the mother and daughter were
described as healthy with no evidence of abnormalities. The concentration
of PCBs in the mothers's milk was foundto be 0.25 ppm, and after
i
j
1 i :
60
GENP 006960
. 775361
WATER PCB-SD0000056721
sulcacion, she stopped nursing her baby [195]. In 1974, Sato and Hasegawa [32] discussed their findings on PCS
sidues in the workers and in the air of pressure-sensitive ("carbonless") copyi^S paper manufacturing plants 2 years after PCB use had been discontinued. A PCB product comparable to Kanechlor 300 was still detected in the workroom air of four of five factories at concentrations ranging - from 0.13 to 4.4 pg/cu m; in one factory PCBs comparable to a mixture of Kanechlors 300, 400, and 500 were found at concentrations ranging from 0.15 to 1.2 Mg/cu m. Concentrations of PCBs in the blood sera of these workers, as measured by GLC, ranged up to 73 ppb, compared to a maximum of about 20 ppb in controls. The authors [32] concluded that the blood PCB concentrations in the workers were still elevated.
PCB concentrations in the blood of three groups of employees with different PCB exposure histories were presented in 1972 by Karppanen and Kolho [198]. The first group of four men and five women had no known occupational exposure to PCBs. The six women of the second group had been exposed while handling PCBs in an analytical laboratory. The third group of eight men and four women had worked, since 1968, in a plant where Aroclor 1242 was impregnated into capacitors. The authors [198] stated that the workroom air of the capacitor factory met internationally accepted limits (presumably <1 mg/cu m) , and that protection of the skin had been given special attention. PCB measurements were made by GLC, using electron capture detection. The unexposed group had blood PCB concentrations of 5.6-12 ppb, the analytical laboratory workers had concentrations of 36-63 ppb, and the capacitor plant workers had concentrations of 74-1,900 ppb. Subcutaneous adipose tissue samples from two of the unexposed workers
61
GENP 006961
775362
WATER PCB-SD0000056722
contained PCBs at 1.5 and 2.3 ppm; PCBa in their blood expressed as concentrations in fat of the blood were 6.6 and 9.9 ppm, respectively. In three capacitor plant workers, adipose tissue samples contained PCBs at 160, 285, and 635 ppm; PCBs in their blood, expressed as concentrations in their blood fat, were 400, 305, and 700 ppm, respectively. All persons examined were in good health. The capacitor plant workers had been under special medical observation but the investigators were unable to detect any biologic effect from the PCBs.
An epidemiologic investigation of 37 refuse workers who were potentially exposed to PCBs emitted from incinerated waste was described by Bumgarner et al [199] in 1973. The control group consisted of 36 workers from a lumber yard. Paired samples of scalp hair and blood were collected. PCB residues in the hair and blood plasma were extracted and analyzed by GLC with electron capture (EC) detection; rough quantitation was by evaluation of five peaks associated with Aroclors 1254 and 1260. The lower limit of detection was 1 ppb. Hematocrit, blood cholesterol, and blood pressure also were determined. PCB residues in the blood plasmas of the controls were detected in four workers and the maximum concentration was 4.2 ppb. Measurable concentrations of PCBs were found in the blood samples of 32 of the 37 refuse workers; the average and maximum concentrations were about 4 and 14 ppb, respectively. The concentrations of PCBs in plasma were not related to duration of exposure, age, or race. PCBs were not detected in hair samples (limit of detection, 1 ppb). Hematocrit, blood cholesterol, and blood pressure values did not change at different PCB concentrations.
775363 62
WATER PCB-SD0000056723
A survey of the health of 34 workers exposed to Aroclor 1242 during -ufacture of capacitors was discussed by Ouw et al [196] in 1976. The Arcelor was an electrical-grade material that contained "no impurities." Breathing zone samples were collected in impingers containing isopropanol. Xt is not clear if all samples were collected from the breathing zones. Nineteen workers were assigned to fill capacitors with Aroclor 1242 heated co 70 C. These workers were exposed to PCBs at 1.08-1.44 mg/cu m. The other 15 workers, located in a different room, were assigned to assemble Aroclor-dipped capacitor components. These workers were exposed to PCBs at 0.32 mg/cu m. None of the 34 workers used protective clothing.
PCBs in the blood were separated by GLC and identified by their retention times relative to aldrin. PCBs were not detected in the blood of 30 control subjects. For the two groups of PCB-exposed workers, averages of measurable blood PCB concentrations are presented in Table III-8.
TABLE III-8
AVERAGE OF DETECTABLE BLOOD PC3 CONCENTRATIONS (ppb) OF TWO GROUPS OF WORKERS
Exposure Group
No. Workers
PCB Retention Time Relative to Aldrin
0.69
1.31
1.47
1.96
Fillers
19 602(19)*
314(17) .
391(13)
475(4)
Assemblers
15
140(14)
100(14)
899(5)
(0)
^Numbers in parentheses are the numbers of workers in whom more than a trace of the PCB peak was detected.
Adapted from reference 196
GENP 006963
63
775364
WATER PCB-SD0000056724
Distribution of PCBa in the blood of workers exposed while filling
the capacitors differed from that of workers who assembled the components.
The higher boiling components were present more frequently and to a greater extent in the fillers.
Twelve of the workers (5 of 19, and 7 of 15) complained of mild
burning and irritation of the face, eyes, and skin, and 5 of these had
eczematous rashes on the hands and legs. One filler had chloracne.
Although individual abnormalities were found in SGPT, SAP, and bilirubin,
the average values for the exposed workers were within normal limits,
Bromsulphothalein retention tests were found to be elevated in four of the
seven fillers whose blood PCB concentrations were >500 ppb. The
investigators [196] reported no evidence of significant adverse responses
to PCB exposure in the workers with blood PCB concentrations below 200 ppb.
Subsequently, "more efficient" exhaust ventilation was installed and
the workers were advised to wear "suitable impervious gloves" [196], Air
measurements, made after the ventilation change, indicated that the fillers
were being exposed to PCBs at 0,18-0.75 mg/cu m and the assemblers at 0.08
mg/cu m.
These were substantial reductions. However, blood PCB
concentrations that were found in 15 workers reexamined 2 months after the
ventilation change did not show any substantial reductions. The
investigators [196] speculated that this might have been because the
workers did not strictly follow the recommendation to wear protective
clothing. Based on a search of chart records, Bahn (HA Sinclaire, written
communication, June 1976) reported a preliminary study of the incidence of
cancer in a group of 51 research and development employees and 41 refinery
64
775365
GENP 006964
WATER PCB-SD0000056725
lant employees at a New Jersey petrochemical facility who were considered likely to have been exposed to Aroclor 1254 for various periods between i949 and 1957. The eight cancers observed in the study population through December 31, 1975 were not significantly more than would be expected (5.7) in a similar sample of the US population [200]. However of the eight cancers, the three melanomas and the two cancers of the pancreas were significantly different from calculated expectations. Some findings of this preliminary investigation were described in a letter from Bahn et al [201] to the editor of the New England Journal of Medicine.
In this preliminary study, PCB exposure histories were based on recollections of two company employees. Exposures to other chemicals could not be ascertained. The expected cancer rates were based on US population data rather than on a rate for the locality of the petrochemical facility. To correct these deficiencies in the preliminary study, a more intensive investigation is being conducted (BN Kightlinger, written communication, November 1976). A substantial change has occurred in the cohort since release of the preliminary report by Bahn and her coworkers, and it seems likely that the findings on this new cohort will differ significantly from those of the preliminary study. The final report is not yet available.
In a study of current and former employees engaged in the manufacture of ?C3s, no cases of malignant melanoma or pancreatic cancer were found from a review of the case histories of more than 300 employees (G Roush, written communication, September 1976). Seven cases of lung cancer were found from the death certificates of 50 former employees compared to an expected number of 2.7. The data are preliminary and were not corrected for age or smoking habits. The final report is not yet available.
006965
65
775366
WATER PCB-SD0000056726
Animal Toxicity Although there have been a few reports of dermal and inhalation
experiments with animals, most of the information on animal toxicity has involved ingestion of PCBs in the diet or by intubation. Several animal experiments have involved oral administration of PCBs for the lifetime of
the animal. These studies have demonstrated chronic changes in the
microscopic anatomy of the liver and other organs, effects on reproduction, embryonic and fetal toxicity, effects on offspring from nursing, and carcinogenic and teratogenic responses.
(a) Inhalation and Dermal Application Studies of PCB Mixtures Absorption and distribution of inhaled PCBs were studied by Benthe et al [97] in 1972. Groups of 4-6 male Wiatar rats were exposed to aerosols of a commercial PCB mixture containing 42% chlorine, Pydraul A 200, commonly used in hydraulic fluids. Absorption and distribution of the PCBs were studied through the measurement of PCB concentrations in liver, brain, and adipose tissue. The aerosols were produced in an aerosol generator at 180 C. The aerosols were cooled, the larger particles were separated out, and the airborne PCBs were introduced into a chamber at a concentration of 30.4 t 3.4 g/cu m. Groups of the rats were exposed for varying periods up to 2 hours. It was found that 15 minutes of exposure was sufficient to attain more than 50% of the PCB concentration of 69.7 jig/g liver wet weight that could be attained with 2 hours of exposure. Consequently, the investigators used an exposure time of 30 minutes to study distribution of PCBs to the tissues. Immediately after 30 minutes of exposure, PCB concentrations were maximal, at about 52 jig/g liver tissue, whereas they were at low
66 775367
l
f
t
i i
\
GENP 006966
f
WATER PCB-SD0000056727
concentrations in the other tissues at 14 yg/g in adipose tissue, and 9 Mg/g in brain tissue. After 24 hours the PCB level in the brain attained a maxinun value of about 18 yg/g and within 36 hours the PCB concentration in the adipose tissue attained a maximum of about 250 yg/g. By 48 hours the concentrations of PCBs in the liver were reduced to about 3 jjg/g and in the brain to about 5 jig/g, whereas the adipose tissue concentrations remained above 200 Mg/g-
Experiments were reported by Rozanova [202] in 1943 in which rats were exposed to a technical mixture of "tetrachlorodiphenyl" and "pentachlorodiphenyl." The mixture, known as Solvol, was a transparent, colorless, oily, very viscous liquid used for filling capacitors. The "tetrachlorodiphenyl" component of the mixture had a distillation range of 220 to 245 C and the "pentachlorodiphenyl" component had a distillation range of 242 to 260 C. The animals were exposed in a 22-liter chamber through which air was `drawn continually at a rate of 1-1.5 liters/minute, after first passing through a glass gooseneck containing the liquid PCBs. Air samples were taken from the chamber from time to time to determine the PCB concentrations. The analytical method was not reported.
Four rats exposed for 3 hours at about 10 mg/liter became uncoordinated and comatose and died within a day [202]. Autopsy findings included liver necrosis and fatty degeneration, cloudy swelling of the epithelial cells of the renal tubules, congestion in the heart and spleen, and necrotic signs in the spleen. Three rats were exposed repeatedly to vapors of Solvol at 0.5 mg/liter. One rat died after eight exposures, and the other two were killed after 11 exposures. Five other rats were repeatedly exposed at 0.25 mg/liter; one was killed after 16 exposures, and
GENP 006967
67
7753
WATER PCB-SD0000056728
the others, which appeared to be in satisfactory condition, were killed
after 69 exposures. In these chronically exposed rats, gross and microscopic findings were similar to, but less marked than, those found in
the acutely exposed animals. In addition, hyperplasia of the Kupffer cells was found in the liver.
Treon et al [203] exposed groups of animals each comprised of 10
rats, 10 mice, 6 guinea pigs, 4 rabbits, and a cat to Aroclor 1242 or
Aroclor 1254 vapors 7 hours/day, 5 days/week for up to 31 weeks. Aroclor
1242 exposures at concentrations of 8,6 yg/liter (0.83 ppm) for 3 weeks,
6.83 Mg/liter (0.66 ppm) for 17 weeks, or 1.9 yg/liter (0.18 ppm) for 31
weeks. Exposures to Aroclor 1254 were at 1.5 yg/liter (0.11 ppm) for 31
weeks or at 5.40 ;ig/liter (0.41 ppm) for 17 weeks. No consistent changes
in mortality, growth, pathology, organ size, liver function, or hematologic
parameters were found in animals exposed to Aroclor 1242. The animals
exposed to Aroclor 1234 vapors showed no changes in growth or mortality but
microscopic evidence of apparently reversible hepatic cellular injury was
found in all species except the cat at both exposure levels. Enlarged
livers were found in the animals exposed at 5.40 pg/liter. An appreciable
incidence of pneumonia was found among the exposed and control animals, a
fact which could have confounded some of the results, but it is important
to note that liver changes, including fatty degeneration, were found in
exposed animals that were free of pneumonia.
Inhalation
experiments
with
the commercial PCB product
"Decachlorodiphenyl" were reported by Berczy et al [98,99] in 1974. The
oral toxicity of this PCB product was investigated by Hunter et al [204] ,
who administered it in the diet to Sprague-Dawley rats at 1,000, 2,000,
68 . 775369
GENP 006968
{
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WATER PCB-SD0000056729
5 000, and 10,000 ppm for 4 weeks. All animals fed Decachlorodiphenyl gained more weight than the controls and had greater liver to body weight ratios. Other effects observed at 10,000 ppm included increased spleen, thyroid, and kidney weights relative to body weights, reduced hemoglobin concentrations, and in males reduced rbc counts and hematocrits.
In one inhalation experiment [98], five male and five female rats were exposed for 6 hours to particles of the PCS product at an average concentration of 2,54 mg/liter. Seventy-eight percent of the particles were in the range of 1-5 fsa in diameter, 17% in the- range of 5-15 ftm, and the remaining 57. were >15 <um. During exposure there were repeated episodes of blinking and sneezing. Signs of irritation disappeared after cessation of exposure. During the subsequent 14-day observation period, food and water consumption and growth of the rats were considered by the authors to have been similar to those of the controls. No gross pathological changes were seen when the rats were killed 14 days after removal from exposure [98].
Subsequently [99], three groups of rats, each consisting of 8 males and 8 females, were exposed 6 hours/day, 5 days/week for 4 weeks at average concentrations of 4, 80, and 777 ^g/liter. A similar group of rats was used as a control. In this experiment, where 85-90% of the particles were in the 1-5 ^an range and 1-3% were >15 jan, no signs of irritation were seen during the exposures at the lower concentrations and growth rates were normal compared to controls. At the highest concentrations, frequent blinking and sneezing were noted during the exposures, and the growth rate of the males was slightly retarded (final body weights of 395 g vs 435 g for controls) . The liver weights, relative to body weight, were increased
GENP 006969
69
775370
'
WATER PCB-SD0000056730
in males exposed at the highest concentration, and in females exposed at the medium and high concentrations. Microscopic findings in the livers of the rats exposed at the high concentration included occasional focal aggregations of mononuclear cells with either parenchymal or periportal distribution, and minimal degrees of periportal hepatocytic vacuolation, and decreased centrilobular or periportal glycogen. These findings were not considered by the authors [99] to be of toxicologic significance. A statistically significant decrease in packed cell and mean cell volumes was found in male rats exposed at the high concentration. In this group there was also a low white cell count due to a decrease in the number of lymphocytes, and increased thrombocyte activity. Blood glucose, SGOT, and serum sodium concentrations were decreased.
Von Wedel et al [205] described in 1942 the results of an experiment
performed to determine the systemic effects of exposure of mice, guinea pigs, and rabbits, by inhalation, ingestion, and dermal application to an
.
unspecified Aroclor. Concentrations and durations of exposure were not specified for the inhalation and ingestion experiments. However, 0.5, 1.0, or 1.5 ml of solutions containing 0.5 g Aroclor/ml were used for the dermal applications. Within 5 days after the dermal applications, small papules and blisters formed on the exposed skin areas and the external epidermal layers became desquamated. In addition, subacute yellow atrophy of the liver with some fatty infiltration was observed. Similar liver lesions were produced In the inhalation experiment.
In 1944, Miller [206] administered Aroclor 1242 to rats, rabbits, and guinea pigs by subcutaneous (sc) injection, by oral intubation, and by dermal and corneal application. The PCB doses ranged from single doses of
| .
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70 775371
GENP 006970
WATER PCB-SD0000056731
69 mg to snail drops (approximately 17 mg) applied daily to the cornea of
rats for 25 days, to 1,380 mg injected daily into rabbits for 10 days.
Fatty degeneration and atrophy of the centrilobular cells of the liver were
the characteristic signs of toxicity. The greatest amounts of liver damage
were seen in guinea pigs, less was seen in rabbits, and the least amount in
rats, regardless of the dose, duration of exposure, or route of
administration. Necrotic lesions were also seen in the skin of animals
that received sc injections; signs of dermal irritation were seen after
applications to the skin. The conjunctival tissue presented no gross
changes when examined under magnification in the living animals. Since the
pathologic changes in internal organs were similar regardless of method of
administration, this experiment indirectly demonstrated that PCBs could be
absorbed through the skin and the eye.
The effects of Solvol applied to the ears of rabbits were reported by
Paribok [207] in 1954. Solvol was applied for 6 hours daily in doses of
0.7 to 3.76 g. A single application caused edema and inflammation of the
ear, and one rabbit died 7 days after the application. With multiple
doses, the animals died after 6-17 days. The dead animals, including the
one that died after the single application, had fatty degeneration of the
livers.
Vos and Beems [208] reported in 1971 on the dermal toxicity of PCBs
in adult female New Zealand rabbits. Three commercial preparations of PCBs
were used: Clophen A60, Phenoclor DP6, and Aroclor 1260, Twenty-seven 1-ml
(118 mg) applications of each of these products (in isopropanol), 5
times/week over 38 days, to the clipped and shaved backs of the rabbits
resulted in various manifestations of toxicity.
GENP 006971
71
775372
if.t
Sr*
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i
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i
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i
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i 1
WATER PCB-SD0000056732
In general, the toxic signs were most pronounced in the Clophentreated animals and least pronounced with Aroclor 1260. Dermal findings included thickening of the skin due to hyperplasia and hyperkeratosis of the epidermal epithelium, and dilation and plugging of hair follicles with keratinous material. Microscopic study of liver sections showed a considerable diversity of lesions, including centrilobular degeneration, focal hydropic degeneration, focal necrosis, atrophy of centrilobular parenchymal cells, cytoplasmic hyaline degeneration, pigmentation of Kupffer cells, and, to a lesser extent, pigmentation of parenchymal cells. Renal damage was found in all PCB-treated animals. The most common findings were hydropic degeneration of the convoluted tubules, with nuclear pyknosis, and bursting and lysis of the tubular epithelial cells [208]. Dilation of the renal tubules, filled with casts of necrotic epithelial cells, was found in half the rabbits. These findings indicate that the dermal application of PCB mixtures causes systemic lesions of the liver and kidneys besides the direct effect on the skin. However, in other studies [19,21,23], it was determined that Clophen A60, Phenoclor DP6, and Aroclors 1248 and 1254 were contaminated, to varying degrees [21], with highly toxic tetra- and pentachlorodibenzofurans.
(b) General Effects of Oral Administration of PCB Mixtures Single-dose oral LD50's of several PCBs reported in rats (JW Cook, written communication, June 1970) generally indicated that as the degree of chlorination increased, the acute toxicity decreased. The more highly chlorinated products (Aroclors 1248-1268) were of approximately equal toxicity (LD50's of about 10 g/kg), whereas the LD50's of the less highly chlorinated products (Aroclors 1221-1242) ranged from about 4 to 9 g/kg.
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The minimum lethal doses of these PCBs applied to the skin of rabbits were
generally in the range of 1-2 g except for 1221 which was in the range of
2-3 g and 1268 which was >2.5 g.
The immunosuppressive activity of Aroclor 1260 was described in 1972
by Vos and de Roij [209] who fed three groups of 12 4-week-old female
albino guinea pigs the PCB at 0, 10, or 50 ppm in their diets for 8 weeks.
Aroclor 1260 was analyzed and found to be free of contamination with
chlorinated dibenzofurans, although it appeared to contain a minor
acnegenic impurity. In each group, six animals received sc injections of
aluminum phosphate-adsorbed tetanus toxoid to stimulate the lymphoid system
(antitoxin production). The other six animals in each group served as
positive or negative controls. Cellulose acetate electrophoresis was used
to determine serum proteins, including gamma-globulins. The gamma
globulin-containing cells in the popliteal lymph nodes were significantly
reduced in the stimulated animals fed PCBs. Serum gamma-globulin levels
were significantly decreased in the guinea pigs stimulated with tetanus
toxoid and fed 10 ppm of Aroclor 1260 in their diet. Increased serum
alpha-globulin levels were found in the stimulated guinea pigs fed either
10 or 50 ppm of the PCB, and significantly increased concentrations of
albumin were found in the sera of both the stimulated and the unstimulated
guinea pigs fed the PCB at 10 ppm. Also, both the absolute and relative
weights of the cervical lymph nodes in the unstimulated group fed 10 ppm of
Aroclor 1260 were significantly reduced whereas those of the mesenteric
lymph nodes in the stimulated guinea pigs fed 10 and 50 ppm of PCB were
significantly increased.
These
findings
indicate
that
some
immunosuppressive effect was produced by the feeding of PCBs. However, the
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decreases of the gamma-globulin levels were not found to be dose-related. No evidence of any PCB-induced change was observed in microscopically examined stained sections of liver, kidneys, adrenals, and skin.
Vos and Van Driel-Grootenhuis [210] reported their studies of the effects of PCBs on the humoral and cell-mediated immunities of guinea pigs in 1972. Three experiments were performed with different protocols. In the first experiment, the authors investigated the humoral immune response of guinea pigs fed 0, 10, 50, or 250 ppm of Clophen A60 in their diets and stimulated with a single sc injection of tetanus toxoid 3 weeks after the feeding regimen began. Suppression of humoral immunity was observed at the 50-ppm level. Microscopic examination of the livers revealed centrilobular degeneration, cellular atrophy, cellular necrosis, and nuclear enlargement. At the 250-ppm level, no antitoxin production was observed.
The diets of guinea pigs in a second experiment [210] contained 0, 10, or 50 ppm of Clophen A60 or 50 ppm of Aroclor 1260. Primary and secondary antigenic stimulations with tetanus toxoid were given after 3 and 5 weeks. The experiment lasted 6 weeks. Suppression of the humoral immune response was observed in groups fed 50 ppm of either PCB product. Decreases in the weights of the thymuses and increases in liver weights were observed at the 50-ppm Clophen A60 level and, to a lesser degree, at the 50-ppm Aroclor 1260 level. The residual liver concentrations of PCBs increased as the dose level and the duration of exposure increased.
In their third experiment, Vos and Van Driel-Grootenhuis [210] fed 30 guinea pigs diets containing Clophen A60 at 0, 50, or 250 ppm. After 3 weeks, the animals were challenged with 0.05 ml of Freund's complete adjuvant followed in 47 days by an injection of 0.1 ml of avian tuberculin
775375
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WATER PCB-SD0000056735
antigen. The animals were killed 2 days later. All animals of the 250-ppm
group died during the experiment, exhibiting retarded growth, atrophy and
depletion of the lymphoid system, and liver damage. Significantly
decreased thymus weights and increased liver weights also were observed,
and total white blood cell counts were reduced significantly.
Bruckner et al [211] administered Aroclor 1242 to rata by oral
intubation to determine its acute and subacute effects. Two groups of six
rats each were given single doses of either 2.5 or 6.0 g/kg of Aroclor
1242. The initial effects observed at both dosages Were the same for the
first 4 hours, ie, diarrhea, decreased spontaneous activity and muscle
tone, decreased response to pain stimuli and mild chromodacryorrhea.
However, during the next 24 hours the group receiving 6.0 g/kg had profuse
diarrhea, adipsia, oliguria, anorexia, erythema of the limbs, lack of
response to pain stimuli, and general weakness. Eventually, ataxia, coma,
and death followed. The condition of the rats receiving the lower dosage
gradually improved after the first 24 hours and was normal at the end of 72
hours.
.
Another group of rats [211] that received single oral doses of 4 g
Aroclor 1242/kg showed weight loss, elevated packed red cell volumes,
increased serum polymorphonuclear leukocytes, crenated red blood cells, and
increased SGOT activities. All organs appeared normal except the livers
and kidneys. The livers exhibited foci of sudanophilic vacuolation. The
kidneys showed widely scattered foci of vacuolated tubular epithelial
cells.
In the subacute studies conducted by Bruckner et al [211] , six rats
were given 100 mg of Aroclor 1242/kg orally every other day for 3 weeks;
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three control rata received 100 mg/kg of peanut oil on the same schedule. Changes observed in the treated rats included increased liver weights, decreased packed red blood cell volumes, Increased SGOT activities and marked increases in liver microsomal hydroxylating and N-demethylating enzyme activities. Microscopic examinations of the livers and kidneys revealed greater Increases in generalized lipid vacuoles than had been found with the acute doses. When single ip doses of 100 mg Aroclor 1242/kg were given to rats, increased N-demethylase and aniline hydroxylase activities were observed after only 24 hours [211].
The effects of lower dietary levels of Aroclor 1242 on rats were reported by Bruckner et al [212], who fed it to groups of six male SpragueDawley rats at concentrations of 0, 5, or 25 ppm for 2, 4, or 6 months. Small reductions in hematocrit and hemoglobin levels similar to those found in other studies by Bruckner et al [211,213] were seen. Urinary excretion of coproporphyrin was significantly increased and dose-dependent increases in liver microsomal hydroxylase activity were measured at the time of each sampling. Similar dose-dependent relationships were found in other experiments [213,214]. Proliferation of the hepatic endoplasmic reticulum was seen after 2 months of ingesting a diet containing 25 ppm of Aroclor 1242; after 4-6 months of such ingestion, lipid vacuolization of the liver was evident.
In 1974, Bruckner et al [213] reported reduced weight gain, hepatic and renal damage, and an Increase in urinary coproporphyrin excretion in rats injected ip with a total of 1.6 g/kg of Aroclor 1242 during a 10-week period. The hydroxylating and N-demethylating activities of the liver ware significantly elevated 24 hours after a single ip injection of 100 mg/kg of
76 -
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Aroclor 1242, with hydroxylating activity showing the greater increase. Cytochromes P-450 and b5 and NADPH-cytochrome reductase activities of the liver all were significantly increased 3 days after dosing. A single dose of 50 mg/kg gave similar but less marked effects, whereas 25 mg/kg produced significant increases in only hydroxylating and N-demethylating activities.
Kimbrough et al [215] described in 1972 some effects of chlorobiphenyl mixtures on the livers of rats. Groups of 3- to 4-week-old male and female Sherman strain rats were given Aroclors 1254 and 1260 at 0, 20, 100, 500, and 1,000 ppm in their diets. Each .group consisted of 10 males and 10 females. Food consumption was measured periodically. The animals were fed the PCBs for 8 months.
One female fed 100 ppm of Aroclor 1260 died after 6 months and two females fed 500 ppm died after 1 and 2 months. Eight females fed the 1,000 ppm diet died in 2-6 months. The rats fed 500 and 1,000 ppm gained less weight than did the controls. At autopsy, livers of the male rats fed Aroclor 1260 weighed significantly more than did livers of control male rats. Livers of the females were larger than normal but the weight differences were not statistically significant, although at 500 ppm the fractions of body weight represented by the livers increased significantly as a result of the reduced body weight gain. Microscopic findings in the livers included hepatocytic hypertrophy, inclusions in the cytoplasm, brown pigment in the Kupffer cells, lipid accumulations, and, at the higher dietary levels, adenofibrosis. The nodular greyish-white areas that represented extensive foci of adenofibrosis consisted of fibroblasts and collagen that surrounded rosettes of epithelial cells [215],
GENP 006977
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..................+ ' " `I'T 'flta stK ttiie siS iS iitsM a sK '' *!!
Aroclor 1254 produced similar results [215]. One female and two male rats died at 500 ppm, but none died at the lower dietary levels, and the rats fed 500 ppm gained less weight than did controls. Ultraatructural changes in the livers of exposed animals consisted of proliferation of the smooth endoplasmic reticulum (SER) and atypical mitrochondria. Similar changes have been observed in other experiments with FCBs [131,212,216 218]. A major difference between the effects of the two products was the much higher incidence of hepatic adenofibrosis at a lower dietary level of Aroclor 1254 (100 ppm). In general, the effects of Aroclor 1254 on the liver were more pronounced than those of Aroclor 1260.
In 1973, Kimbrough et al [219] reported the results of a study conducted to determine whether morphologic changes produced in the liver would regress after ingestion of PCBs was stopped. Fifty male SPF Sherman strain rats were given Aroclor 1254 at 500 ppm in their diets for 6 months, and then were returned to normal diets. Groups of five rats were killed 0, 1, 2, 3, 4, 6, 8, and 10 months after ingestion of PCBs had been discontinued. The livers and adipose tissues of the 10-month group were analyzed for PCBs. Control animals were used in all evaluations and were fed only laboratory chow.
The livers of exposed animals killed when exposure to Aroclor 1254 was discontinued were enlarged and most of the 40 livers studied microscopically showed enlarged hepatocytes, increased lipid contents, and adenofibrosis. A brown pigment was seen in the Kupffer cells and in other macrophages of 15 livers. Small adenoflbrotlc lesions consisting of glandular epithelial cells that formed ducts surrounded by slight amounts of fibrotic tissue were seen; larger lesions had more extensive fibrosis
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and contained collagen. Similar findings had been reported earlier by Kimbrough et al [215] and both in the areas of adenofibrosis and in othevise normal hepatic tissue, Kimbrough [220] later reported finding small clusters of glandular type cells, resembling those of pancreatic tissue in general appearance and staining characteristics, in 15 of 36 rat livers with adenofibrosis. The cells stained red with the stain used for esterase, and developed a blue granular appearance with the stain used for protein bound tryptophan. These staining reactions were suggestive of those of salivary gland tissue to the author. The cells may have been derived from either ductal or vascular epithelium, but there is no evidence to substantiate either suggestion [220].
Signs of regression of the adenofibrotic lesions were not noted except for the disappearances of epithelial cells from the centers of the lesions [219]. Liver weights did regress to normal after 10 months without PCB exposure, but the lipid accumulation and the hypertrophy of the hepatic cells remained unchanged. Analysis of adipose tissues from the final group of rats killed showed that the PCB levels ranged from 924 to 1688 ppm (mean, 1192 ppm) . Liver PCB levels ranged from 17.3 ppm to 26.2 ppm (mean, 22.7 ppm). The PCB concentrations in the adipose tissue and livers of the control animals were less than 1.0 ppm. The authors [219] were unable to decide whether contamination of Aroclor 1254 with dibenzofuran was responsible for the observed liver lesions [219]. .
Kimbrough and Linder [221] reported in 1974 the results of a PCBfeeding experiment which they undertook to induce adenofibrotic lesions in the livers of BALB/cJ inbred male mice, ie, lesions similar to those previously observed in rats fed Aroclors 1254 and 1260. Two hundred mice,
GENP 006979
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5-6 weeks old, were distributed randomly into 4 groups of 50 each. Two
groups were fed.a ground diet containing 300 ppm of Aroclor 1254. At the
end of 6 months, one of these exposed groups was placed on a PCB-free diet
while the other exposed group continued on the test diet for another 5
months. The other two groups served as controls and were fed the plain
ground laboratory diet for the entire 11 months. The average PCB intake
was 49.8 mg/kg/day in the mice fed the PCB diet for the entire 11-month
period.
Livers of 45 of the 58 surviving control mice were found to be
normal. The other 13 had focal round-cell infiltrates and sometimes small
areas of necrosis and fibrosis. Skin abscesses, usually near the groin,
were identified in all 13 control mice with hepatic round-cell infiltrates.
These skin lesions were thought to be abscesses of the preputial glands.
In comparison, 10 hepatomas were identified in 9 of the 22 survivors in the
group fed the PCB diet for 11 months. These tumors consisted of well-
differentiated hepatocytes, relatively uniform in size but usually smaller
than the surrounding liver cells. They were well circumscribed and
surrounded by compressed hepatic parenchymal cells or strands of fibrous
tissue. In the larger tumors, there were areas in which the sinuses were
dilated and filled with a pink-staining amorphous material. No metastases
were seen on gross Inspection of the organs, although no detailed
screening, such as serial sectioning of the lungs, was undertaken. Only
one small hepatoma, composed of well-differentiated hepatocytes, was
identified among the 24 survivors fed the PCB diet for only 6 months. The
authors [221] noted that the mouse strain used in this study rarely
develops hepatomas spontaneously. 80
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Adenofibrosia was identified in the livers of the mice subjected to the 11-month PCB diet. These lesions, according to the authors [221], may or may not be precursors of malignant lesions. They were seen in several areas of each liver as fibrosis and as glandular formations of proliferated epithelial cells replacing parenchymal cells. They formed ducts which produced mucus and which were surrounded by connective tissue of varying abundance.
Allen and Abrahamson [216] reported on morphologic and biochemical changes in the livers of rats given Aroclors 1248, 1254, and 1260 at 1,000 ppm in their diets for 6 weeks. A control group was fed unsupplemented chow. Each group contained 24 rats. Four rats were killed after 1,3,7,14,21, 28, and 42 days of exposure. White blood cells, hemoglobin (Hb), hematocrit (Hct), differential white cell count, total serum proteins, and blood urea nitrogen (BUN) were measured at each interval. Selected tissues were prepared for microscopic examination and the livers were homogenized and analyzed for cytoplasmic protein, DNA, and RNA. Liver microsomes were examined for aryl hydrocarbon hydroxylase, nitroreductase, N-demethylase, and nitrophenylacetate hydroxylase activities, and for cholesterol content.
All of the PCB-dosed rats failed to gain weight. The most severe effects were noted with Aroclor 1248, followed by Aroclors 1254 and 1262. All blood samples showed increases in Hb and Hct, with no changes in the white blood cell counts. Neutrophils were increased in the sera of all treatment groups. There were no changes in BUN or in total serum protein levels. Organ weights in all of the experimental rats constituted higher percentages of total body weights than in controls; the livers showed four-
GENP 006981
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WATER PCB-SD0000056742
fold increases in weight in all PCB-doaed groups. The Increased liver
weights were discernible after only 1 day of exposure. Liver hypertrophy
was attributed to proliferation of SER, development of large concentric
arrays of membranes, and increases in lipid droplets within the cytoplasms
of the affected cells. Aroclor 1248 was the most, and 1262 the least,
toxic PCB product as judged by changes in liver histology. Liver
homogenates contained increased concentrations of protein and RNA, and
decreased concentrations of DNA. These changes were seen within 2 weeks
after initiation of feeding Aroclors 1248 and 1254; the protein and nucleic
acid concentrations then either leveled off or decreased after 4-6 weeks.
Aroclor 1262, however, did not induce these effects until 4 weeks after the
beginning of feeding; the initial changes were followed by reversals [216].
' Liver microsomal fractions had increased protein and phospholipid
concentrations. These changes occurred earlier in the rats fed Aroclor
1248 and 1254 than in the Aroclor 1262-fed animals. Microsomal
nitroreductase activity, expressed on the basis of microsomal protein, was
variable in the animals fed Aroclors 1248 and 1254; however, all animals
fed Aroclor 1262 had progressive increases in nitroreductase activity. N-
demethylase activity Increased early in the experimental period and
Increased progressively in all treatment groups as the exposures continued.
Aryl hydrocarbon hydroxylase, glucose-6-phosphatase, and other esterase
activities increased initially, followed by continuous declines in activity
in the groups fed Aroclors 1248 and 1254. The rats fed Aroclor 1262 had
similar, but less marked, changes. When enzyme activities were expressed
as activity per total liver, all showed marked Increases. After 6 weeks,
other degenerative changes in the liver occurred, such as dissolution of ' 82
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Che concentric arrays of membranes, vesiculation of the endoplasmic reticulum, and accumulation within the cytoplasm of lipid droplets that had developed during the hypertrophic phase of the intoxication [216] .
Allen et al [222] administered PCBs (Aroclor 1248) and polychlorinated terphenyls (Aroclor 5460) to rhesus monkeys. Sixteen male monkeys were distributed into three groups. Group 1 consisted of six animals and was fed a basal diet supplemented with 300 ppm of Aroclor 1248. Group 2 consisted of six animals fed a basal diet containing 5,000 ppm of Aroclor 5460. The remaining four monkeys constituted the control group and were fed the standard colony diet. Each animal had access to 400 g of diet daily. The physical status of the animals was evaluated daily and "complete" blood studies were performed biweekly. Approximately 10 g of liver tissue were removed from each animal during the 6th week (via laparotomy) and during the 12th week (at necropsy) for biochemical and microscopic evaluation.
Animals fed Aroclor 1248 lost an average of 26% of body weight; those receiving Aroclor 5460 lost an average of 19% of body weight. Gross changes seen in the animals fed Aroclor 1248 included loss of hair from head, neck, and back, puffy faces, edematous lips, and swollen eyelids with purulent exudates around the eyes. These changes were seen within 1 month; similar, but less marked changes were seen in the animals fed Aroclor 5460
[222].
Hematologic changes developed gradually. After 3 months, hemoglobins had decreased by about 2 g/100 ml, and hematocrits had diminished from about 40% to 33%. Total white blood cell counts did not change; however,
GENP 006983
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there was a shift to the left in the differential count. Total serum
proteins decreased by about 1.5-2 g/100 ml, and there was a gradual shift
in the albumin/globulin ratio of the serum protein. No changes were seen
in SGOT or BUN. Both experimental groups had similar patterns of changes
[222].
'
At necropsy, both groups of animals showed extensive alopecia,
acneiform lesions of the skin, subcutaneous edema, liver hypertrophy with
fatty infiltration, and gastric mucosal hypertrophy and hyperplasia. Liver
hypertrophy was attributed mainly to proliferation of the hepatocytic SER.
Gastric hypertrophy was characterized by thickened gastric mucosa, numerous
large cystic areas filled with mucin, and hyperplasia. Ulceration was
seen, as was invasion of the underlying mucosa by glandular-type epithelial
cells [222].
The authors [222] noted that, biochemically, the decreases observed
in the DNA concentrations of the livers of both experimental groups
reflected the hypertrophic cells observed microscopically, and the
Increases in protein and HNA were said to be compatible with the
proliferated SER. Levels of microsomal protein per gram of protein were
not markedly altered, but decreases in the specific activities of esterase,
aniline hydroxylase, nitroreductase, and glucose-6-phosphatase became
apparent within 6 weeks, and persisted. N-demethylase activity was
Increased at each examination.
The results of a toxicity study conducted on four young male rhesus
monkeys fed Aroclor 1242 at concentrations of 3, 10, 30, or 100 ppm were
reported by Bell [223], McNulty [94], and in a communication written in
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March 1977 by WP McNulty. All four monkeys on these diets died within 9
months. The monkeys had facial swelling, red and swollen eyelids,
conversion of all secretory-type cells of the stomach to mucous cells,
growth of mucous glands into the muscular walls of the stomach, multiple
ulcers in the stomach, atrophy of the thymus gland, and either
disappearance of sebaceous glands or conversion of these glands to keratin
cysts, particularly in the eyelids.
.
Allen et al [104] and Allen and Norback [224] found gastric
hypertrophy and hyperplasia and focal ulceration of the stomach lining in
adult male rhesus monkeys fed single doses of 1.5 or 3.0 g of Aroclor 1248.
(c) Studies Involving Individual PCB Isomers
In 1972, Vos and Notenboom-Ram [225] discussed the comparative
toxicities of dermally applied 120-mg doses of 2,2',4,4',5,5'-
hexachlorobiphenyl and Aroclor 1260. The PCBa, dissolved in isopropanol,
were applied 20 times to the clipped and shaved backs of three groups of
four rabbits each, 5 times/week for 4 weeks. The control group received
only isopropanol. The Aroclor 1260 sample was found to be "free'* of
chlorinated dibenzofurans (limit of detection, 1 ppm), and because of the
nature of the chemical reactions utilized in the synthesis of
2,2',4,4',5,5'-hexachlorobiphenyl,
Dermal applications of these PCBs
resulted in early macroscopic skin lesions and morbid liver changes similar
to those found by Vos and Beems [208]. These liver lesions included
centrilobular degeneration and liver cell atrophy, focal cytoplasmic
hyaline degeneration of the hepatocytes, enlarged nuclei, loss of glycogen
and proliferation of SER. The authors [225] concluded that, although the
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major acnegenic action of crude PCB mixtures results from the presence of
chlorinated dibenzofurans, PCBs have acnegenic actions of their own.
Hansell and Ecobichon [217] described the effects of a series of
chemically pure chlorobiphenyls on rat liver morphology. Biphenyl and a
series
of isomerically 'pure mono-, di-, tetra-, hexa-, and
octachlorobiphenyls of known composition were administered intraperltoneal
(ip) injections in daily doses of 50 mg/kg to groups of seven young male
Woodlyn strain Wistar rats for 3 consecutive days. The rat-s were killed 4
days after the final injections had been made and sleeping times after
phenobarbital administration had been determined. The major microscopic
alterations observed were proliferation of the hepatocytlc SER, changes in
the rough endoplasmic reticulum, and Increased numbers of lipid droplets
and microbodies. However, in the rats administered isomerically pure hexa-
and octachlorobiphenyls, there were additional changes in hepatic
morphology, including large numbers of hepatocytes with cytoplasmic
vacuoles and small foci of necrosis involving five or six cells. Biphenyl
and 2,2*-dichlorobiphenyl appeared not to Induce extensive proliferation of
the SER, but with the other compounds the SER proliferation appeared to be
related to the degree of chlorination, especially to the presence of a chlorine in the 4 and/or 4' positions,
The investigators [217] also injected groups of seven rata ip with daily doses of 100 mg/kg of either 4-mono-, 4,4*-di-, or 2,5,2*,5'tetrachlorobiphenyl for 7 days; all rats from each group were killed 24 hours after the last injections. This regimen caused more pronounced alterations in hepatocytic ultrastructure than those observed after the 3day experiments. Marked proliferation of SER and increased numbers of
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microbodies and lipid droplets were noted, as were a large number of necrotic foci, ' centrilobular necrosis, and proliferation of biliary ductules. The most severe lesions were seen in the group receiving i,4'dichlorobiphenyl. There was not the increase in hepatic weight and cell size noted by other authors [219,226]. Hansell and Ecobichon [217] observed that this apparent anomaly may have been due to the duration of PCB administration, only 3-7 days, and to the relatively low dosages.
Allen et al [226], in a series of experiments, studied the toxicity of 2,2 ' ,5,5'-tetrachlorobiphenyl in rats and rhesus monkeys. In the first experiment, 5-week-old rats were separated into five groups consisting of five males and five females each. After being fasted overnight, each of these groups was administered by gavage a single dose of one of the following amounts of the compound dissolved in corn oil: 0, 0.5, 1.0, 1.5, or 2.0 g/kg. Each dose had a total volume of 1 ml. After the dose had been given, blood was taken for complete blood counts. Eighteen of the d0 PCB-dosed rats died within 3 days. The dead animals included all chose given 2.0 g/kg, 7 rats from the group given 1.5 g/kg, and 1 rat from the 1.0 g/kg group. The rats were observed for 21 days after which complete blood counts were performed and the surviving animals were killed and necropsied. The major pathologic changes observed in the animals that died were narked regressions of lymphocytes in the spleen and lymph nodes and of cortical thymocytes. With the exception of hemorrhage and atrophy of the thymus, 'which were related to the decrease in the cortical thymocytes, and enlargement of the liver and kidneys, all tissue samples were normal when compared with those from the nonexposed group.
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The second experiment was conducted to determine the effects of hepatic microsomal enzyme activity on the responses of male Sprague-Dawley rats to 2,2 ', 5,5'-tetrachlorobiphenyl [226], The rats were separated into 6 groups of 10 animals each. Group 1 was a positive control given four ip injections of 75 mg/kg of the microsomal enzyme inhibitor, SKF 525A, at 8hour intervals. Group 2 was given four daily sc injections of 75 mg/kg of phenobarbltal. Group 3 was the general control. Groups 4, 5, and 6 received 1.25 g/kg of the chlorobiphenyl in 1 ml of corn oil by gastric intubation; group 5 was dosed with the chlorobiphenyl 24 hours after 4 days with daily sc doses of 75 mg/kg of phenobarbltal. Group 6 received 75 mg/kg of SKF 525A ip 2 hours prior to administration of 2,2* ,5,5'tetrachlorobiphenyl, and every 8 hours thereafter for 24 hours. Within 4 days, all the rats in group 5 and 50% in group 4 had died whereas none had died in group 5, which was pretreated with phenobarbltal. The findings that pretreatment with phenobarbltal allowed complete survival of rats after an LD50 dose of the PCS, whereas pretreatment with SKF 525A caused 100% mortality, Indicated to the investigators that metabolic transformation by endoplasmic reticulum enzymes resulted in deterification [226].
The third experiment was performed to compare the differences between the responses of rats to 2,2', 5,5'-tetrachlorobiphenyl and Aroclor 1248 [226] . Twelve male rats were placed in three groups of four animals each; group 1 was fed 100 ppm of Aroclor 1248 in its diet, group 2 was given 100 ppm of the 2,2' ,5,5' isomer in its diet, and group 3 (control) was fed the staple ground meal diet. After 4 weeks of these feeding regimens, the rata were fasted for 24 hours, killed, and necropsied; blood was also collected
88 ' 775389
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at this time. There were no detectable differences in general appearance, fccc consumption, activity, growth rate, or blood chemistries between the two experimental groups and the control group. The only significant difference at autopsy was an increase in liver weight as a percentage of body weight of the animals fed Aroclor 1248: 4,46 t 0,11%, compared with " 3.38 0.13% for those fed 2,2',5,5'-tetrachlorobiphenyl and 3.0 t 0,12% for the controls. Proliferation of the endoplasmic reticulum within the hepatic cells was observed in the Aroclor 1248-fed animals. The Ndemethylase activity and the cytochrome P-450 content of the microsomal fraction of homogenized liver from the Aroclor 1248-fed rata were increased whereas the activity of aniline hydroxylase and glucose-6-phosphatase in this fraction had decreased. There were increases in the concentrations of protein and RNA and a decrease in the DNA content of the liver homogenates from the Aroclor-fed animals. The livers of rats fed the isomer had similar but less marked changes in concentrations of protein, RNA, and DNA. The mean concentration of microsomal protein in liver was identical with that of the controls but was more variable. A significant increase in the mean activity of N-demethylase was found.
The fourth experiment [226] was performed to determine the effects of 2,25,5 '-tetrachlorobiphenyl on non-human primates. Seven adult male rhesus monkeys were given 18 mg/kg of the PCS isomer dissolved in 2.5 ml of corn oil and three controls were given 2.5 ml of com oil, all by gavage after a 24-hour fast. Complete blood counts had been done on each animal prior to intubation. Immediately after treatment, the animals were placed in metabolism cages and their urine and feces analyzed for 2,2'',5,5'-
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tetrachlorobiplienyl by GLC. On the 14th day of the experiment the animals were fasted for 24 hours, killed, and necropsied. Tissues were taken for light and electron microscopy and GLC. No overt clinical effects were seen in the treated monkeys. Over 12% of the PCB was recovered unmodified in the feces but only minute amounts were present in the urine. Only the adipose tissue and adrenals had high PCB assays t and microscopically, except for a moderate proliferation of hepatocytlc SER, all tissues were normal. DNA was slightly decreased in liver homogenates of exposed animals and hepatic microsomal cytochrome P-450 was Increased.
Torok [227], in 1976, reported a study of pregnancy in NMRI mice treated with 2,2'-dichlorobiphenyl. The mice were separated into three groups, with group 1 (37 mice) serving as the control; group 2 (18 mice) received the PCB in oral doses of 375 mg/kg/day on days 1-3 of gestation, and group 3 (37 mice) received 750 mg/kg/day on the same schedule. Administration of the PCB at either level resulted in longer intervals from breeding to parturition: 18.2 days for controls, 19.4 days for mice treated with the PCB at 375 mg/kg/day, and 21.8 days in mice treated at 750 mg/kg/day. There also were reductions in the numbers of dams with litters and in the mean litter size. Reductions were greatest in group 3. The authors [227] concluded that the effects were due to delayed Implantation,
(d) * Reproductive and Teratogenic Effects of PCB Mixtures Curley et al [101] studied the transplacental movement of PCBs in rats. Three groups of 90-day-old female rats were paired with male rats of the same age. All were fed standard laboratory chow by the authors, who designated the day of insemination as day 0. Aroclor 1254 was given in
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doses of 0, 10, and 50 mg/kg in peanut oil (presumably by oral intubation) once a day on days 7 through 15 of pregnancv to groups 1, 2, and 3, respectively.
On the 20th day after insemination, fetuses were taken by Caesarean section from three rats of each PCB-exposed group and from two control rats. The fetuses from each experimental group were divided into two lota and analyzed as duplicate samples for PCBs. Ten rats from each of the three experimental groups were allowed to deliver spontaneously. When the offspring were 5 days old, six mothers from each exposed group and two from the control group were separated from their litters for several hours and then returned for 1 hour of nursing. The contents (milk) of the pups' stomachs were analyzed for PCBsi Litters from three rats in each experimental group were allowed to survive-until weaning at 21 days of age. These baby rats then were kil led and their tissues analyzed for PCBs by GLC with EC detection [101].
The rats subjected to Caesarean section had normal fetal complements, in both size and number, and in the rats allowed to deliver spontaneously there were no significant differences in average litter size and weight among the three groups. However, the three groups, with 0, 10, or 50-mg/kg doses of Aroclor 1254, had 0, 1, and 4 stillbirths on the average, respectively [101],
Analyses of the tissues of the Caesarean-delivered pupa showed measurable levels of PCB-derived components in the exposed groups only. The mean PCB concentrations were <0.12, 0.63 t 0,06, and 1.38 t 0.06 ^g/g, respectively, for groups 1, 2, and 3. Although the PCB dose for group 3 was five times that of group 2 (50 vs 10 mg/kg Aroclor 1254) , the average
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amount of PCB-derlved components measured in the fetuses from these two groups differed by only two-fold. The authors suggested that the PCB distribution between the mothers and their fetuses may not have been uniform and that a partial (unspecified) barrier may have existed [101],
Livers were increased in size and had enlarged hepatocytes in 15 of 21, and 15 of 20 weanling rats from groups 2 and 3, respectively. Some rats from group 3 showed vacuolization of the hepatocytic cytoplasm (10 of 20) , and 5 of 20 exhibited bile duct proliferation. Morphologic changes in the liver were more pronounced at the higher dose [101].
PCB-derived components were detected in litter-pooled milk at mean concentrations of <0.75, 20.60 t 1.59, and 66.34 t 8.36 jxg/g in groups 1, 2, and 3, respectively. The authors [101] concluded that the morphologic changes identified in the livers of exposed weanling rats were probably caused by PCBs transmitted to the pups in the milk from the dams [101],
Reproductive effects of feeding Aroclors 1254 and 1260 to Sherman strain rats for two generations were reported by Linder et al [228] in 1974. In preliminary experiments, the two mixtures were fed to groups of 10 females at 100 and 500 ppm in the diet. Two similar groups served as controls. The diets, fed for 67 days before the first mating, were continued through gestation and lactation. After weaning of the first litters, the parents continued to be fed the diets. After being fed PCBs for a total of 186 days, they were again mated and the diets fed through the second gestation and lactation. Feeding Aroclor 1254 at 500 ppm resulted in only 4 first litters being bora (2 alive), with no survivors to weaning. Consequently, feeding Aroclor 1254 at 500 ppm was discontinued. With Aroclor 1254 at 100 ppm, there was little indication from either the
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first or second mating of reduced fertility, or increased death in utero or
during the nursing period. Aroclor 1260 fed at 100 ppm for 67 days had no
apparent effect on reproduction, litter size, or survival of the first
litters; however after being fed for 186 days, only 5 second litters were
born from 9 mated females, compared to 9 out of 10 in the controls. At 500
ppm, Aroclor 1260 resulted in more pups dead at birth in first litters,
reduced second litter size, and fewer litters being weaned (3 of 8 first
litters; 2 of 6 second litters).
'
Subsequently, Linder et al [228] fed groups of 20 female Sherman rats
Aroclor 1254 at 1, 5, 20, and 100 ppm and Aroclor 1260 at 5, 20, and 100
ppm. Appropriate control groups with similar numbers of rats were used.
The experimental plan was similar to that described above except that the
FI generation pups continued to be fed the F2 generation diet until they
reproduced the F2 generation. The first matings of the FI generation were
after they were exposed to PCBs in utero, in milk, and in the diet for 125
129 days. The Fl generation rats fed Aroclor 1254 at 20 and 100 ppm were
maced a second time after a total of 274 days of PCB exposure.
Rats exposed to Aroclor 1254 at dietary levels of 20 ppm or more had
fewer pups in their litters than the controls [228]. There were also fewer
F2 generation pups than controls. Second litters bom from rats fed 100
ppm of Aroclor 1254 had increased mortality and markedly decreased mating
performance. Dietary levels of 5 ppm Aroclor 1254 and 100 ppm Aroclor 1260
had no effect on reproduction in rats exposed through two generations.
Liver weights were increased in 21-day-old Fl male weanlings at 1 ppm of
Aroclor 1254 and in either sex of Fl and F2 weanlings at 5 ppm or higher of
both Aroclors 1254 and 1260.
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Villeneuve ec al [229], in 1971, wrote about fetotoxic effects of Aroclors 1221 and 1254 in rabbits. Twenty-four mature female rabbits were divided into six groups each comprised of two control and four experimental does. Experimental animals were given the Aroclors orally at 1.0 and 10 mg/kg/day beginning after mating and continuing through gestation.z They were killed 28 days after mating. Neither Aroclor had a fetotoxic effect at either dose level. Liver weights expressed as percentages of body weight were significantly heavier in the does fed 10 mg/kg Aroclor 1254 than in controls (4.29 vs 2.79%). Liver weights of the other experimental does and of all fetuses were not significantly different from controls.
In another experiment reported by Villeneuve et al [230] , 16 mature female rabbits were separatedinto four groups and, after mating, were dosed orally with 0, 12.5, 25, or 50 mg/kg of Aroclor 1254 daily for the first 28 days of gestation. The 50-mg/kg group had three pregnancies.z One pregnant female died on the 11th day and contained nine fetuses. A second one died on the 17th day and contained six resorption sites. The third female aborted three dead fetuses on the 28th day. Two rabbits in the 25og/kg group had normal fetuses. A third rabbit aborted her litter on the 28th day and died. The four animals in this group showed an average weight loss of 26 g and liver weights found at autopsy 29 days after mating averaged 5.11% of their body weights. Autopsies were performed on the fetuses of the two rabbits which had conceived in the 12.5-mg/kg group; the first rabbit had two normal fetuses, with six resorption sites, while the second aborted two fetuses onthe 27th day and was found on autopsy to contain one partially resorbed and two dead fetuses. The two dead fetuses obtained on autopsy showed subcutaneous cephalic hemorrhages and had
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asymmetric skulls. Average weight gain of the females during pregnancy was 265 g, and their liver weights averaged 6.03% of their body weights. Controls gained 654 g during pregnancy, and their livers averaged 2.66% of their body weights.
In their third experiment, Villeneuve et al [230] gave each animal in three groups of six female rabbits 25 mg/kg Aroclor 1254 in corn oil (orally). Controls received com oil alone. . A control group and one exposure group were dosed from day 1 through day 28, and another control and an exposure group were dosed from day 7 through day 28. Administration of Aroclor 1254 at 25 mg/kg/day from day 1 through day 28 resulted in abortions in two of four rabbits. Their average weight gain was 245 g and liver weights averaged 6.03% of their body weights (controls, 531 g weight gain; liver weights, 2.65% of body weight). In the second group administered PCBs, one of four rabbits aborted. Average weight gain was 156 g and the liver weights averaged 4.82% of the body weights.
PCB concentrations in various tissues of six rabbits and their fetuses, chosen at random from the above groups, were determined by Grant et al [231]. Concentrations of PCBs were higher in the livers of the fetuses than in their mothers: 5.4 vs 2.1 ppm at a dose of 1 mg/kg; 78.1 vs 69.5 ppm at 12.5 mg/kg; and 375.3 vs 124.2 at 25 mg/kg. In other tissues, PCB concentrations were generally less in the fetuses than in the dams.
Allen et al [232] in 1974 presented evidence of possible fetotoxicity in a short term PCB feeding experiment with 12 adult female rhesus monkeys. The monkeys ranged in age from 7 to 10 years and had an average weight of 5.6 kg. Each previously had delivered at least one infant and the menstrual cycle of each had been recorded for at least 2 years. Six of the
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monkeys were fed an unspecified diet containing 25 ppm of Aroclor 1248 for 2 months. The other six monkeys were controls. After 2 months, the PCBexposed animals were placed on PCB-free diets of commercial monkey chow.
The monkey which had consumed the largest amount of PCBs died on the 128th day of the experiment [232] . At the beginning of the 5th month, ie, 3 months after the test animals had been removed from the PCB-containing diet, the remaining five test monkeys and the six controls were mated again. Three PCB-exposed monkeys were thought to have conceived since each showed the characteristic post-conceptual bleeding, lack of the subsequent menstrual period, and an enlarged uterus. Two either aborted or reabsorbed their fetuses during the 2nd month of pregnancy and the third monkey delivered a well-developed but smaller-than-normal (375 g 1 g vs 544 g 101 g) infant. High concentrations of PCBs were found in the adipose tissues and adrenals of this infant with means of 27.7 and 24.4 fig/g, respectively, as compared to a range from 0.01 to 0.98 jig/g in the other infant tissues analyzed. The PCB levels in the placenta averaged 0.9 pg/g,
and 50 fig/g in Che mother's adipose tissue. Two additional attempts were
made to breed the nonpregnant females during the next 5 months. Only the controls became pregnant and all delivered normal infants. Six of the monkeys were fed an. unspecified diet containing 25 ppm of Aroclor 1248 for 2 months. The other six monkeys were used as controls. After 2 months, the PCB-exposed animals were placed on PCB-free diets of commercial monkey chow.
In 1976, Barsotti et al [233] and Allen and Barsotti [234] reported their findings on reproductive dysfunction in female and male adult rhesus monkeys fed Aroclor 1248 in their diets. One test group of female monkeys
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received 2.5 ppm and the other group received 5.0 ppm of Aroclor 1248 in a
commercial diet. The control group, containing 12 females and 6 males, was
fed the commercial diet alone. Females received 200 g, and the males
received 300 g of their respective diets daily. Food left in the feeding
cups at the end of the day was removed and weighed to determine the daily
intake. After the end of the first 6 months, the average PCB intakes were
180 and 364 mg for females fed the 2.5- and 5.0-ppm diets, respectively
[233].
'
Some of the exposed females began to exhibit the characteristic skin
and blood chemistry signs of PCB intoxication within 2 months. At 6
months, all exhibited these signs in varying degrees. Menstrual cycles
were irregular and menstrual bleeding was excessive and prolonged [233] .
The conception rates for the control females and for those fed the
2.5-ppm Aroclor diet were 12 of 12 and 8 of 8, respectively, whereas 6 of 8
females fed the 5.0-ppm Aroclor diet conceived [233]. All 12 of the
control group pregnancies resulted in normal births, compared to 5 and 1,
respectively, for the exposed females fed the 2.5- and 5.0-ppm diets.
Three of the eight fetuses of monkeys fed the 2.5-ppm Aroclor diet were
resorbed shortly after conception. Profuse uterine hemorrhaging was
observed rather than the implantation bleeding which usually occurred 17
days after conception, according to the authors [233]. The two females
from the group fed the 5.0-ppm diet who did not conceive initially were
bred five times without success. Of the six females'of this group that did
become pregnant, three aborted at 46, 67, and 107 days of gestation; one
fetus was resorbed, one was stillborn, and one delivered normally. The six
live infants bom to PCB-fed mothers had body weights that were less than
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normal for the colony by one to two standard deviations. These infants began showing signs of PCS toxicity (acne, swollen eye lids, increased skin pigmentation) after nursing their mothers for less than 2 months [234]. In samples obtained from three of their mothers after the infants developed the poisoning signs, the milk contained PCBs at 0.154-0.397 ppm, and the milk fat from a fourth mother contained 16.44 ppm. Three of the infants died 44-112 days after birth.
The effects of Aroclor 1254 on reproductive performance and fetal integrity were evaluated in beagle dogs and Hormel miniature swine by FL Earl et al (written communication, 1976). Aroclor 1254 was administered orally in capsules as a solution in corn oil to 46 purebred beagle bitches once daily after the 1st day of gestation. Ten bitches were given 0.25 mg/kg/day, 16 were given 1 mg/kg/day, and 20 were given 5 mg/kg/day. Sixteen untreated bitches served as controls.
The data presented show that Aroclor 1254 at 5 mg/kg/day significantly interfered with reproductive performance and was teratogenic in the beagle. When Aroclor 1254 was administered at 0.25 and 1.0 s/kg/day, no effects on reproduction were observed but the incidence of patent fontanelles in the offspring of the 1.0-mg/kg/day group was increased sharply. Dosage at 5.0 mg/kg/day resulted in 45.5% resorptions (4-fold increase over the control rate) and an average of only two live pups per litter. Patent fontanelles were present in 50% of the offspring.
Earl and his coworkers fed Aroclor 1254 to Hormel miniature swine in doses of 1.0 (4 sows), 10.0 (6 sows), and 30.0 (7 sows) mg/kg/day for 21 days before breeding and throughout gestation. Five sows served as controls. The 1-mg/kg/day dose produced a statistically significant
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percentage of fetal resorptions (23%). Increasing the dose to 10 mg/kg/day lowered the fertility rate to 50% (80% in controls) and increasing the dose to 30 mg/kg/day lowered the fertility rate to 43%. Cleft palate and syndactyly in three feet were observed in one fetus from the group fed 10 mg/kg/day. At this dose level, there was also a significant decrease in survivability with only 71% of the offspring alive after 5 days. At the 30-mg/kg/day dose, 14 of the 15 implantations were resorbed and teratogenic abnormalities were present in 100% of the observed fetuses. Cleft palates, syndactyly, and patent fontanellea were the teratogenic effects observed. The fact that pigs are normally born with closed fontanelles increases the signficance of the teratogenic findings.
(e) Studies on Mutagenicity and Cytotoxicity To evaluate the effects of PCBs on the testes of rats, Dikshith et al [235] administered, by oral intubation, 50 mg/kg/day of Aroclor 1254 dissolved in corn oil* to a group of 18 adult male Sprague-Dawley rats for 7 consecutive days. A control group of 18 rats received corn oil without PCBs. Three rats from each group were killed 1, 7, 15, and 30 days after the last PCB administration. The testes and epididymises were separated and weighed, as were the livers. Microscopic, histochemical (acid phosphatase), and cytogenetic examinations were performed. Rats used for cytogenetic examination were injected ip with colchicine 2 hours before being killed and the chromosomes in testicular tissues were examined. No effects on weight or gross appearance of either the testes or epididymis were noted, nor was there evidence of atrophy or hypertrophy of the testes. The only structural changes noted in the testes of the exposed group was a proliferation of interstitial tissue cells. These cells showed
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an increase in acid phosphatase activity, which, according to the authors [235], denoted a change from particulate enzyme localization in testicular interstitial cells of the controls to a disseminated, diffuse localization in the testes of the exposed group.
Cytogenetic analyses showed similar chromosomal configurations in both the control and the exposed groups. In the PCB-treated rats, some apparently sporadic abnormal chromosomes were seen in a few of the metaphase figures; chromosomal abnormalities also included breaks, exchange figures, chromatin bridges at anaphase, and chromosome fragments. The significance of these findings was unclear to the authors [235].
Green et al [236] looked for mutagenic effects in the bone marrow and spermatogonial cells of male Osborne-Mendel rats fed various doses of PCBs. Rats were given Aroclor 1242 either in single oral doses of 1,250, 2,500, or 5,000 mg/kg or in multiple oral doses of 500 mg/kg/day for 4 days. Aroclor 1254 was administered orally in daily doses of 75, 150, or 300 mg/kg for 5 days. The Aroclors were mixed with corn oil, except the 5,000 mg/kg dose of Aroclor 1242, which was given undiluted. Controls were fed uncontaminated corn oil. The animals were given Colecimid (a colechicine derivative) at 4 mg/kg 24 hours after PCB dosing was completed and they were killed 3 hours later.
Aroclor 1242 produced no statistically demonstrable evidence of chromosomal damage in bone marrow cells at doses of 1,250 or 2,500 mg/kg, or at the 500-mg/kg dose level [236]. At 5,000 mg/kg, there appeared to be an increase in the number of chromosomal abnormalities. However, since most of the changes occurred in one animal, the findings were not considered to be significant. Aroclor 1254 did not produce statistically
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significant numbers of chromosomal abnormalities in bone marrow cells at
any dose level tested. A statistically significant number of chromosomal
abnormalities was not identified in spermatogonial cells from rats fed
Aroclor 1242. Spermatogonial cells from rats given Aroclor 1254 were not
examined since the results with the more acutely toxic Aroclor 1242 were
negative. All observed chromosomal lesions were single chromatids. The
authors [236] did not exclude the possibility of point mutations since the
procedures used in this experiment would not have detected such damage.
Green et al [237] also investigated the possible induction of
dominant lethality in rats given Aroclor 1242 or Aroclor 1254 by oral
intubation.
Except for the positive controls, results showed
nonreproducible positive effects.that were not related to dose or stage
sensitivity. The authors concluded that the two Aroclors did not appear to'
be mutagenic.
Wyndham. et al [116] performed the "Ames" bacterial test for
mutagenicity on a variety of PCBs, using Salmonella tvphimurium mutant
strain TA1538. A comparison was made of the mutagenic potentials of
Aroclor 1254 , 2,2',5,5*-tetrachlorobiphenyl, Aroclor 1268, Aroclor 1221,
and 4-chlorobiphenyl. The results showed clearly that as the degree of
chlorination decreased', the mutagenic potential increased. A concentration
of 100 vg of 4-chlorobiphenyl in the test medium gave over 2,000 revertant
colonies/plate. The more highly chlorinated biphenyls showed very little
activity as mutagens.
Hoopingarner et al [238] studied the toxicities of various Aroclors
at 50 ppm in the culture medium of Chinese hamster cells, and found
increasing toxicity (measured by cell population survival) with decreasing
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chlorination. Aroclor 1016 appeared to be disproportionately cytotoxic, on
the basis of its chlorine content, suggesting to the authors that this
product contained certain toxic components in higher proportions than
either Aroclor
1232
or Aroclor 1242, which it resembled
chromatographically. Aroclor 1254 at 100 ppm showed no apparent effect on
the chromosomal integrity of human lymphocytes in vitro.
Popper et al [239] studied the effect of hepatic microsomal
biotransformation systems from control mice and from mice treated with PCBs
on the mutagenic potentials of the primary carcinogen N-methyl-N'-nitro-N-
nltrosoguanldine (MNNG), and the secondary carcinogen dimethylnitrosamine
(DMN). Hepatic microsomes were isolated from male Swiss-Webster mice that
had been given 500 mg/kg of Aroclor 1254 4 days earlier, and from untreated
control mice. The mutagenicities of MNNG and DMN were assayed by a
bacterial auxotroph reversion test using Bacillus subtills.
Microsomes prepared from the livers of the PCB-treated mice had 2-3
times as much cytochrome P-450 activity as the controls [239]. DMN added
directly to the cultures was not mutagenic at concentrations as high as 300
mM. However DMN was converted to a mutagen when exposed to such microsomes
in the presence of an NADPH-generating system. When MNNG was incubated
with isolated mlcrosotnes, its mutagenic activity was reduced. The authors
concluded that Isolated hepatic microsomes can modify the biologic
activities of mutagens and that the hepatic microsomal biotransformation
system could play a key role in chemical mutagenesis.
(f) Studies on Tumorigenesis
Kimbrough et al [218] distributed 400, 21- to 26-day-old weanling,
Sherman strain, "COBS" female rats randomly into two equal-size groups.
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Half of the rats were fed a plain commercial laboratory chow. The other 200 were fed laboratory chow containing 100 ppm of Aroclor 1260. The dosed group of rats was fed the PCB diet until 6 weeks before they were killed at the age of 23 months. Autopsies were performed on these rats as well as those that died before the exposures ended.
Microscopic examination was completed on 184 dosed animals and 173 controls. From a-few to multiple elevated tan nodules were found on the liver surfaces of 170 PCB-fed rats. The nodules varied from 0.1 to several cm in diameter. Only one such abnormality was found in the controls. Of the tumors, 26 of those in exposed animals and the 1 from the control animal were hepatocarcinomic; the other 144 experimental animals had hepatocellular nodules that were described as characteristic of neoplastic nodules or synotnously, hyperplastic nodules. The authors [218] said "neoplastic nodules are part of the spectrum of response to hepatocarcinogens and must be included in the evaluation of tumorigenesis." Tumors identified and analyzed from other organs had no unusual features; no apparent differences in incidence were observed between the experimental and control groups [218].
Evidence of PCB-induced hepatocarcinomas was reported by a group of Japanese investigators in 1972 [240] and in 1973 [241]. Nine groups of 12 male dd mice were fed a commercial stock diet supplemented with 100, 250, or 500 ppm of Kanechlors 300, 400, or 500. A control group of eight mice was fed the stock diet. All mice were given water ad libitum. After 32 weeks, the animals were starved for 18 hours, killed, and examined macroscopically for tumors. Seven of the 12 mice fed Kanechlor 500 at 500 ppm developed hyperplastic liver nodules and five had well-developed
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hepatocellular carcinomas. None of the mice fed Kanechlor 500 at lower concentrations or Kanechlor 400 or 300 at any concentration developed hepatocarcinomas.
In 1973, Kimura and Baba [242] described neoplastic changes in the livers of rats exposed to Kanechlor 400. Thirty 10-week-old rats were separated into an experimental group of 10 males and 10 females and a control group of 5 males and 5 females. The experimental group was fed a diet supplemented with olive oil containing various concentrations of Kanechlor 400. The control group received an olive oil-supplemented diet. The diet of the experimental group of rats contained 38.5 ppm of Kanechlor 400 for the first 4 weeks, followed by 77 ppm for 8 weeks, 154 ppm for 3 weeks, 308 ppm for 3 weeks, and 616 ppm for 8 weeks. Body weights were checked weekly and showed rapid decreases during the 616-ppm feeding period; for this reason the Kanechlor 400 content of the diet was reduced to 462 ppm for the next 32 weeks. The total feeding period for the experimental and control animals was about 58 weeks (400 days).
All rats that Ingested total doses of more than 700 mg of Kanechlor 400 developed hypertrophy of the liver [242]. Pale brown nodules were present on the parietal and cut surfaces of the livers of female rats that had ingested more than 1,200 mg of PCBs. However, none of the male rata had such hepatic nodules, despite having ingested equal or greater amounts of Kanechlor 400. On microscopic examination, the livers of female rats were observed to have fatty degeneration and multiple adenomatous nodules that appeared to be benign neoplastic lesions. Males did not develop such neoplastic lesions; however, their livers did exhibit fatty degeneration. Lung abscesses, pneumonia, splenic atrophy, and intracranial abscesses were
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found frequently in the experimental group. The authors [242] thought that resistance to infection was lowered in the rats fed Kanechlor 400.
A formal rulemaking hearing was convened August 20, 1976 by the US Environmental Protection Agency on its proposed toxic pollutant water effluent standards for PCBs (Federal Register 42:6532-55, February 2, 1977). Part of the testimony concerned comparative studies in which groups of 100 male and female Charles River rats were fed 1, 10, and 100 ppm of Aroclors 1242, 1254, or 1260 for 24 months. The survival of the rats was poor and the experiment was said to have been inconsistently reported. A reevaluation of the pathology slides revealed the occurrence of liver tumors (hepatomas and cholanglohepatomas) in the rats fed any one of the three Aroclor products. The incidence of liver tumors in the rats dosed at 100 ppm was 3/20 for Aroclor 1242, 6/27 for Aroclor 1254, and 7/27 for Aroclor 1260, compared with 0/20 for the controls. In addition to the tumors there was a high frequency of nodular hyperplasia. The incidence of nodular hyperplasia at 100 ppm was 8/20 for Aroclor 1242, 13/27 for Aroclor 1254, and 7/27 for Aroclor 1260, compared with 1/23 for the controls. Nodular hyperplasia in the rats dosed at 10 ppm occurred in 2/10 for Aroclor 1242, 3/26 for Aroclor 1254, and 9/23 for Aroclor 1260, and 1/23 for the controls. The incidence of tumors of the pituitary gland also was elevated in each treated group.
Correlation of Exposure and Effect (a) Absorption, Metabolism, Excretion, and Body Burdens It has been demonstrated in experimental animals that PCBs can be
absorbed into the blood from Inhaled air [97] and from the digestive tract
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[50,51,95,96]. Qualitatively, the effects in experimental animals from
absorption by either route were similar [98,99,202-206]. When PCBs were
applied to the skin, certain effects, such as those on the liver, were
similar to those obtained when PCBs were ingested or inhaled [205-208].
Thus, it appears that PCBs were also absorbed by this route.
In experimental animals, most PCB isomers were metabolized in varying
degrees to more polar compounds such as hydroxylated derivatives
[41,48,49,51-56,58-81,85,87]. The more highly chlorinated isomers were
metabolized slowly and accumulate in the tissues [41,50,51,55,61-64,66,82
84,96,103,107-110]. The hydroxylated derivatives were excreted in the
bile, urine, and milk [41,48,50-56,58-61,63-66,69,71-80,85]. Unmetabolized
compounds were excreted in feces, milk, and hair [41-44,50,51,53-56,100
102], and traces were found in urine [42,51-55,57-62,103-105].
In man, the metabolism of PCBs has not been studied. However,
finding that PCB isomers that are difficult to metabolize become
concentrated in residual PCBs of tissues from the general population, from
persons who have ingested PCBs, and from those with occupational exposure
suggests that man metabolizes, eliminates, and stores the compounds in ways
similar to those of animals [7,36,136,168,171-175]. Determinations of PCBs
or their metabolites in urine or feces of humans have not been reported.
PCBs have been'found in human hair [102,142]. Excretion in human milk of
PCBs with compositions similar to those in blood, has been reported in
association with general environmental exposures and following ingestion
and occupational exposures [143,144,168,192]. These findings of PCBs in
human hair and milk also suggest metabolism and excretion similar to those
of animals.
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GENP 007006
WATER PCB-SD0000056767
Because PCBs are widespread in the environment, detectable concentrations have been found in tissues and body fluids of a substantial portion of the US population (36,102,134,135,137,140,144]. Detectable concentrations have been found in up to 62% of blood serum samples, with concentrations ranging up to 30 ppb [137]. In emaciated patients, blood PCB concentrations as high as 100 ppb have been found [140]. PCB concentrations in about three-fourths of adipose tissue samples from the general population were <1 ppm, and the remainder were mostly in the range of 1-2 ppm [36,136]. Usually the PCB isomers found in blood and adipose tissue have been penta-, hexa-, and heptachlorobiphenyls [7,135,136] , and a high correlation was found between the concentrations in these two tissues [141]. PCB isomers in cord blood were qualitatively identical to those in maternal blood [138]. PCB isomers excreted in human milk were similar or identical to those in blood [168], and the concentrations in milk were positively correlated* with adipose tissue concentrations [143]. In human milk samples from the general US population, PCB concentrations up to 13 ppm (fat basis) have been reported (EP Savage, written communication, February 1977).
These concentrations of PCBs in blood, adipose tissue, and milk of the general US population arise from dietary intakes estimated to be of the order of 10-20 ng/day [46] and from inhalation of air that may contain up to 100 ng/cu m [26,38].
(b) Irritation Effects and Chloracne The first reports of adverse effects of PCBs on workers included chloracne [120,123,130] , digestive disturbances [ 123] , irritation of mucous membranes [ 120,123,130] , and impotence [ 123]. The exposures associated
GENP 007007
107
7?s408
WATER PCB-SD0000056768
Because .PCBs are widespread in the environment, detectable concentrations have been found in tissues and body fluids of a substantial portion of the US population [36,102,134,135,137,140,144]. Detectable concentrations have been found in up to 62% of blood serum samples, with concentrations ranging up to 30 ppb [137]. In emaciated patients, blood PCB concentrations as high as 100 ppb have been found [140]. PCB concentrations in about three-fourths of adipose tissue samples from the general population were <1 ppm, and the remainder were mostly in the range of 1-2 ppm [36,136]. Usually the PCB isomers found in blood and adipose tissue have been penta-, hexa-, and heptachlorobiphenyls [7,135,136], and a high correlation was found between the concentrations in these two tissues [141] . PCB isomers in cord blood were qualitatively identical to those in maternal blood [138]. PCB isomers excreted in human milk were similar or identical to those in blood [168], and the concentrations in milk were positively correlated' with adipose tissue concentrations [143]. In human milk samples from the general US population, PCB concentrations up to 13 ppm (fat basis) have been reported (EP Savage, written communication, February 1977).
These concentrations of PCBs in blood, adipose tissue, and milk of the general US population arise from dietary intakes estimated to be of the order of 10-20 ng/day [46] and from inhalation of air that may contain up to 100 ng/cu m [26,38].
(b) Irritation Effects and Chloracne The first reports of adverse effects of PCBs on workers included chloracne [ 120,123,130] , digestive disturbances [123], irritation of mucous membranes [120,123,130], and impotence [123]. The exposures associated
107 775409
GENP 007008
WATER PCB-SD0000056769
terphenyls was used; the PCB used in the other process [189] was not described, but extensive skin exposure from wearing PCB-soiled clothing and from immersion of unprotected hands into the PCB mixture was described.
A case of chloracne that developed in an Australian worker after exposure to Aroclor 1242 at concentrations of 1-2 mg/cu m was reported by Ouw et al [196]. The PCB preparation was heated during a capacitor-filling process. Complaints of process workers Included irritation of the face, eyes, and skin. Eczematous rashes were also found on their hands and legs.
In the reports of chloracne development in occupations involving PCBs (where environmental concentrations of PCBs were measured) [125,130,186 189,196 ], the sampling and analytical methods did not distinguish between vapor and particulate forms of the PCBs. However, a common factor in many of these reports [ 186-189,196] was the use of heat in the process which would tend to generate PCB vapors.
In their study of capacitor and PCB manufacturing plants in Japan, Hasegawa et al [191] found that concentrations of PCB vapors (or particles <0.1 ym in diameter) exceeded the concentrations of PCBs in particles >0.1 im. in diameter. The compositions of PCBs in the particulate were similar to those in the PCB preparations in use, but the less highly chlorinated compounds were concentrated in the vapors. In this study, where PCB vapors ranged from 0.026 to 0.965 mg/cu m and PCBs in the larger airborne particulates ranged from 0.19 to 0.650 mg/cu m (maximum total PCBs of 1.6 mg/cu m), dermal ailments included a brown chromodermatosis of the hands and chloracne. The workers had been exposed to PCBs from <1 to 20 years.
Meigs et al [190] described a process in which chloracne developed where the exposures had to have been to PCB vapors. The PCB which was used
GENP 007009
109
775410
WATER PCB-SD0000056770
as a heat-exchange medium was not described, but PCB concentrations were reported to be about 0.1 mg/cu m in the workroom air where the workers were
exposed. Under these conditions, chloracne developed after a minimum of 5
months of exposure. Chloracne has also been studied in connection with determinations of
PCB concentrations in blood. Hara et al [192,193] found whole blood PCB concentrations of 7 to 300 ppb in Japanese workers engaged in capacitor filling. About 40% of these workers had chloracne and 13% had irritation of the skin. Kitamura et al [194] found PCBs at 320-820 ppb in blood samples from Japanese workers engaged in capacitor manufacture. Skin ailments, including chloracne, were found in 10 of 13 workers studied. Inoue et al [195] found chloracne in a man exposed to PCBs in a silkglossing factory who had a concentration of about 200 ppb of PCBs in his blood, but they [195] found what were described as relatively mild skin abnormalities in 28 other workers engaged in similar processes who had blood PCB concentrations mostly under 100 ppb (2 had concentrations >100 ppb). Ouw et al [196] concluded from their study of capacitor workers that no adverse effects were found in workers with blood PCB concentrations <200 ppb.
Studies of PCB-exposed workers where chloracne has not been found include those of Levy et al [197] , Karppanen and Kolho [198] , and Bumgarner et al [199]. In the study by Karppanen and Kolho [198] , workers who had been exposed to PCBs for 4 years in a capacitor-impregnating operation had PCB concentrations of 74-1,000 ppb in samples of their blood. The environmental exposure concentrations of PCBs were reported to meet "internationally accepted standards." Other factors of the work situation,
775411
110
WATER PCB-SD0000056771
such as the skin protection used, were not reported. In the study by Levy et al [197], workers who had been exposed to PCBs for 2.5-18 years had concentrations of PCBs in samples of their blood ranging from 36 to 286 ppb. PC3 exposure concentrations at the time of the study were 0.013-0.264 mg/cu m. Although some of the workers complained of throat or eye irritation, and some skin rashes were found, no cases of chloracne were seen. From the description of the work situation, it is unlikely that skin exposure to liquid or solid PCBs was an important factor in the total exposure of these workers. In their study of refuse workers, Bumgarner et al [199] found blood PCB concentrations to be 4-14 ppb. One possible source of exposure of these workers was airborne incinerator effluents, and it is unlikely that additional exposure from skin contact occurred.
Although skin exposure was unlikely in these two reports [197,199] where chloracne was not found, skin exposure is not necessary for chloracne to develop. Chloracne has been observed in Japanese people estimated to have ingested total PCB doses of 0.3-4 g [146,164-167], and chloracne-like lesions have been produced in experimental rhesus monkeys fed PCBs at 3 ppm in their diets [222] .
Thus, although eliminating exposure of the skin through engineering controls and using appropriate protective clothing and work practices will reduce the total absorption of PCBs, these practices will not necessarily eliminate chloracne. The data Indicate that chloracne may occur with exposures to PCB vapor concentrations as low as 0.1 mg/cu m for several months, and with PC3 concentrations in the blood of about 200 ppb.
GENP 007011
Ill
775412
WATER PCB-SD0000056772
J O U tW K lU i
~ ivt.uiuu
(c) Effects Referable to the Liver
Some clinical and autopsy findings in Yusho, the disease that
occurred after ingestion of PCB-contaminated rice oil by humans, were
indicative of liver injury [155-158,179-181]. These findings included
changes in liver cell anatomy considered consistent with microsomal enzyme
stimulation and increased SAP activity. Effects that persisted for several
years Included decreased concentrations of iron and bilirubin in the serum
[155,179] and increased serum concentrations of triglycerides. The latter
were found to increase with residual concentrations of PCBs in the serum
[180].
.
The maximum amounts of PCBs consumed by individuals manifesting these
effects were estimated to have been of the order of 3-4 g total Intake over
several months [165]. For two Yusho patients a daily PCB consumption of 67
Mg/kg for 3 months was estimated [167]. The maximum intake would have been
of the order of 50 ppm in the diet or 0.5-1 mg/kg/day. For comparative
purposes, absorption of PCBs from inhalation during maximum occupational
exposures that have been reported (10 mg/cu m) probably did not exceed 0.15
mg/kg/day.
The extent to which PCB consumption was responsible for the effects
on the liver is not known since the contaminated oil also contained PCDFs
[20,160] in quantities that could have resulted in a maximum PCDF
consumption of 20-50 mg. Autopsy findings 1-3 years after the poisonings
indicated unusually high concentrations of PCDFs (0.3-2.5 Mg/g) relative to
PCBs (3.5-5.6 Mg/g) in liver fat [ 160].
Although most animal feeding experiments have been conducted with
dietary levels of PCBs that are much higher than those ingested by Yusho
112
' 775413
GENP 007012
'
WATER PCB-SD0000056773
patients, others have been conducted with dietary PCB levels that seem to confirm the Yusho findings. Experiments have been reported with various commercial PCB mixtures (Aroclors 1242, 1254, 1260, and Clophen A60) added to the diet at 1-10 ppm [101,209-212,215,228,233]. These experiments demonstrated increased liver weights at all concentrations, dose dependent stimulation of microsomal enzyme activities, detectable proliferation of the SER at concentrations of 10-100 ppm, and other microscopic changes including enlarged hepatocytes, hepatocytic vacuolization, and, with prolonged exposures, development of adenofibrosis.
At high PCB concentrations (>1.5 mg/cu m), inhalation experiments with animals have demonstrated increased liver weights [98,99,202,203] . Microscopic changes similar to those seen from PCB ingestion were found in livers of rats after inhalation of Aroclor 1254 at 1.5 mg/cu m or more [203] , and from other commercial preparations (Decachlorodiphenyl and Solvol) at much higher concentrations (>4 mg/cu m) [99,202].
These data from the Yusho poisonings and from animal experiments indicate that hepatic effects seen in human are similar to those seen in animals. They also Indicate that some commercial preparations may be less severe liver poisons than others, but the data are not definitive in this regard. The ingestion experiments demonstrated increased liver weights from feeding PCBs at 1 ppm, and increasing evidence of liver injury as dietary PCB levels were increased. A dietary. level of 1 ppm may be considered roughly equivalent to a daily intake of the order of 0.01-0.02 mg/kg, which would be somewhat similar to the intake from inhaling PCBs at 1 mg/cu m.
GENP 007013
113
775414
WATER PCB-SD0000056774
*w , m . w - v f Ti <* i m m k m a m k tm M im n * ** -*# #
Several reports of occupational exposures to PCBs have involved the liver in various ways [123,125,127,186,190,191,197,198,200].
In the earliest reports of PCB toxicity [123,135,127], the PCBs were mixed with chlorinated naphthalenes. The mixtures caused many cases of chloracne and, in some cases, jaundice. Liver cirrhosis with superimposed yellow atrophy was found in at least one fatality [125]. Similar findings have not been reported where exposures were to only PCBs in the absence of chlorinated naphthalenes.
Mention of nausea and digestive disturbances in some reports [123,197] may have indicated liver injury. In the study by Schwartz [123], neither liver function test findings nor exposure concentrations were reported. In the Levy et al report [197], liver function tests (SAP, SGOT, SGPT, total bilirubin) performed at the time of the study did not indicate current liver injury. The workers had been exposed to unidentified PCBs at 0.013-0.264 mg/cu m, and blood PCB concentrations were 36-286 ppb. Even though there were no findings of current liver injury, these investigators' [197] examination of past medical records showed occasional findings indicative of slight liver injury (elevated serum enzymes, triglycerides, and uric acid). A report of a worker who was removed from further exposure after experiencing nausea on exposure to an askarel containing Aroclor 1254 was not accompanied by liver function test results or exposure concentration data (In the Matter of General Electric Company, File No. 2833, New York State Department of Environmental Conservation, 1975).
More conclusive studies of liver function were reported by Meigs et al [190] , Hasegawa et al [191] , Hara et al [ 192,193] , and Ouw et al [196]. Of the workers exposed to vapors of an undefined PCB at 0.1 mg/cu m in the
114 775415
GENP 007014
WATER PCB-SD0000056775
study by Meigs et al [190], liver function tests were performed on seven. Findings in six of the workers were normal and, in the other one, cephalin flocculation and thymol turbidity tests were on the borderline of abnormality. Hasegawa et al [191] found some changes in liver function tests (increased SGOT, SGPT, and SAP, arid decreased serum cholinesterase and lipids) of 99 workers exposed to Kanechlors but the investigators considered that only the decreased serum lipids were significant. PCB exposure concentrations at the time- of the study were 0.045-1.6 mg/cu m. The workers had exposure histories of <1 to 20 years. PCB concentrations in blood samples of the workers averaged 370 ppb.
Kara et al [192] did not find evidence of a correlation of serum triglyceride concentrations with blood PCB concentrations during the first year after the work with PCBs was discontinued. However, when the same workers were studied 2 years after stopping work with PCBs, the proportion of workers with elevated serum triglycerides increased as residual blood PCB levels increased [193]. The effect was particularly prominent in workers with residual blood PCB concentrations >50 ppb. In a study of 34 workers exposed to Aroclor 1242 in capacitor manufacture, Ouw et al [196] found individual abnormalities in SGPT, SAP, and serum bilirubin, but average values for the group were normal. Bromsulphalein retention tests were elevated in four workers. Ouw et al [ 196] considered that there were no adverse responses in workers with blood PCB concentrations below 200 ppb . The PCB exposure concentrations were 0.32-1.44 mg/cu m.
No evidence of impaired liver function was found in other studies [186,194,195,198] where PCB exposures were reported as: Aroclor 1254 at 5-7 mg/cu m for 2-4 years [186] : Kanechlors at >0.25 mg/cu m [195] : and
GENP 007015
115
775416
WATER PCB-SD0000056776
unidentified PCBs at <1 mg/cu tn for 4 years [198].
Evidence relating to impaired liver function from occupational
exposures to PCBs is generally consistent with findings in Yusho patients
and in animal studies that indicated some effects could be expected from
PCB intakes equivalent to PCB inhalation at about 1 mg/cu m. The
occupational exposure studies show occasional evidence of liver injury in
workers exposed at concentrations of 0.013-0.264 mg/cu m [197], 0.1 mg/cu m
[190], 0.045-1.6 mg/cu m [191], and 0.32-1.44 mg/cu m [196]. Whether the
observed effects occurred with exposures at the lower end of all these
ranges is not known.
The occupational exposure studies also showed delayed recovery of
normal serum triglycerides after exposures to PCBs stopped [193], The
elevated serum triglycerides were related to the higher residual blood PCB
concentrations, and these in turn were related to the years of exposure.
Residual PCBs have repeatedly been shown to be the more highly chlorinated
isomers and those
metabolized
with
greater
difficulty
[7,36,51,83,103,110,135,136].
Summaries of effects of PCBs on humans and animals are presented in
Tables III-9 and III-10, respectively.
\
? ; | I% l ? ; `
Carcinogencitv, Mutagenicity, Teratogenicity, and Effects on Reproduction (a) Carcinogenicity There is extensive evidence for formation of arene oxide
intermediates during the metabolism of PCBs by several species including rhesus monkeys [51,68,69,74,75,81,115,116,118], Arene oxide formation was also proposed as a plausible intermediate in the metabolism of the slowly
. 775417 116
GENP 007016
WATER PCB-SD0000056777
metabolized 2,2',4,4',5,5'-hexachlorobiphenvl [70,79].
Binding PCB
metabolites to nuclear components of liver cells has been demonstrated on
administration of PCBs to monkeys [51] , and to rats [81] , and by in vitro
experiments [51,82,86,116,117] . This information is sufficient to arouse
suspicions that PCBs could have carcinogenic potential in humans.
Hepatomas were produced in 170 of 184 examined female rats fed
Aroclor 1260 at 100 ppm from 3-4 to 23 months of age [218], and in 9 of 22
BALB/cj male mice fed Aroclor 1254 at 300 ppm for 11 months [221]. The
tumors found in the rats included 26 hepatocarcinomas and 144 neoplastic
nodules. Only one liver tumor, a hepatocarcinoma, was found in 173 control
rats.
In another report (Federal Register 42:6532-55. February 2, 1977) ,
dose-related incidences of liver tumors were reported in rats fed Aroclors
1242, 1254, or 1260 at 1, 10, and 100 ppm in the diet for 24 months. No
liver tumors were reported in rats fed the diets containing PCBs at 1 ppm.
Only one tumor, a hyperplastic nodule (neoplastic nodule), was found in 23
controls. Neoplastic nodules were found in the livers of rats fed the diet
containing 10 ppm of PCBs (2/10, 3/26, and 9/23 for Aroclor 1242, 1254, and
1260, respectively). Higher tumor incidences were found when diets
containing PCBs at .100 ppm were fed (11/20, 19/27, and 14/27 for Aroclors
1242, 1254, and 1260, respectivelv) and the tumors included hepatomas and
cholangiohepatomas (3, 6, and 7 for Aroclors 1242, 1254 and 1260,
respectively) . In this experiment the incidence of pituitary tumors was
high in PCB-fed rats.
In a study sponsored by the National Cancer Institute, Aroclor 1254
was fed to groups of 24 rats at 25, 50, and 100 ppm in the diet. No liver
GENP 007017
117
775418
WATER PCB-SD0000056778
tumors were found in the controls, in the experimental females at any dose
level, or in experimental males fed PCBs at 25 ppm.
However,
hepatocellular carcinomas were found in a male rat fed Aroclor 1254 at 50
ppm and in two males fed the PCB at 100 ppm. The data also indicated that
the incidence of leukemias in males was dose-related (3/24 in controls; 8/24 in rats fed 100 ppm).
Kanechlors have also been found to produce liver tumors when fed to mice and rats [240,241,242], Of 12 mice fed Kanechlor 500 at 500 ppm for
32 weeks, 7 developed neoplastic liver nodules and 5 had well-developed hepatocellular carcinomas [240,241], In this experiment which had only 12
mice/group and continued for only 32 weeks, liver tumors were not found with Kanechlors 300 and 400 or with lower dose levels of Kanechlor 500.
However in another experiment [242], Kanechlor 400 fed to 10 male and 10
female rats for 58 weeks did produce liver tumors in the females. In this
experiment the amounts fed (38-616 ppm) varied from time to time, but were
in the 308-616 ppm range for the last 43 weeks.
These findings from animal studies indicated to NIOSH that PCBs have
potential carcinogenic activity in humans. They indicate, but do not conclusively demonstrate, with the dietary levels used, that the less
highly chlorinated mixtures (Aroclor 1242 and Kanechlors 300 and 400) have less carcinogenic potential than the more highly chlorinated mixtures
(Aroclors 1254 and 1260 and Kanechlor 500). However, all PCB mixtures
adequately tested in rats and mice have shown carcinogenic activity. The Intakes of PCBs at the lowest dietary level that has produced tumors in
rats (10 ppm) would be somewhat comparable to intakes from occupational
exposures at 5-10 mg/cu m. However PCBs are slowly eliminated from the
775419
GENP 007018
WATER PCB-SD0000056779
body and Che higher chlorinated compounds may .accumulate in the body for years. Thus animal experiments that are limited to 2 vears by the life span of the animals may not be informative relative to workers exposed for up to 45 years.
In humans, there are no adequate studies to confirm or deny carcinogenicity although preliminary data suggest that among Yusho patients, deaths due to cancers exceed expectations [160,161] and preliminary studies of two occupationally exposed groups in the US indicate that the occurrence of certain cancers may be excessive (HA Sinclaire, written communication, June 1976; G Roush, written communication, September 1976). However, the two reports are not consistent as to the types of cancers found to occur more frequently than expected.
(b) Mutagenicity Several PCBs and PCB mixtures, including the 4- and the 2,2' ,5,5 isomers and Aroclors 1221, 1254, and 1260, were subjected to the "Ames" test for mutagenicity [116],. Although 4-chlorobiphenyl had mutagenic activity in this test, the more highly chlorinated PCBs showed very little activity. Aroclor 1254 did not cause significant chromosomal changes in the testes of rats after it was administered for 7 days at 50 mg/kg/day [235]. In another experiment [236], neither Aroclor 1254 administered at 300 mg/kg/day for 5 days nor Aroclor 1242 administered at 500 mg/kg/day for 4 days produced chromosomal aberrations in spermatagonial or bone marrow cells of rats. These mixtures also did not produce any evidence of dominant lethal mutations in rats [237]. Although PCBs have little mutagenic potential, they may alter the mutagenicity and carcinogenicity of other compounds by stimulating microsomal enzyme activities [239].
GENP 007019
119
775420
WATER PCB-SD0000056780
(c) Teratogenicity PCBs have been found in embryonic and fetal tissues of humans [139,168] and experimental animals [101] after introduction of PCBs into the maternal body, demonstrating that the potential for direct teratogenic effects exists. Several experiments have been conducted with rats [101,228], rabbits [229], monkeys [232], and dogs and pigs (FL Earl et al, written comnunication, 1976) that are relevent to a discussion of PCB teratogenicity. In some of these experiments, the PCBs were administered by gavage and doses were reported in mg/kg; in other experiments, the PCBs were reported as ppm fed in the diet. For purposes of relative comparison, 50 ppm In the diet can be equated to 1 mg/kg/day. This is the order of magnitude of the maximum rate of PCB intake by Tusho patients. Animal experiments have used PCBs in dietary-equivalent amounts of 1-2,500 ppm. In most experiments with PCBs administered in amounts equivalent to dietary levels of 100 ppm or more, fetotoxicity (resorptions, absortions) has been such that teratogenic effects may have been masked [101,228,229]. In the two-generation feeding study of rats by Linder et al [228], no terata were reported. This study covered Arodor 1254 in the concentration range of 1 100 ppm and Aroclor 1260 in the range of 5-100 ppm. Although terata were not reported, Aroclor 1254 concentrations of 20-100 ppm resulted in reduced litter sizes. In rhesus monkeys [232], feeding Aroclor 1248 at 2.5 and 5 ppm caused abortions in some cases and lower than normal birth weights, but no terata were reported. In dogs, terata were not found in pupa born from dams fed the equivalent of 12 ppm in the diet, but were present when 48- or 200-ppm equivalents were fed. Sows fed the equivalent of 50 ppm in the same experiment had high rates of resorptions and, at 10-30 times this
120 775421
GENP 007020
1 j ; I
1 i '
j
j i
WATER PCB-SD0000056781
level, terata were definitely present in the piglets (FL Earl et al, written communication, 1976).
Although there were retarded intrauterine growth and signs of PCB toxicity in Yusho babies at birth, no terata were reported [149,159,176,182,183]. A normal baby was born to a woman exposed to PCBs in her work. The PCB exposure concentrations were not reported but the PCB concentration in her blood was 25 ppb at the time the baby was born.
These studies indicate that PCBs have teratogenic potential for humans. However, the terata observed in animals occurred at levels at or above doses equivalent to the maximum doses of the Yusho patients and at intake rates 3-4 times greater than intakes expected from inhalation at maximum reported occupational exposures.
(d) Other Effects on Reproduction Feeding rats Aroclor 1254 at 5 ppm or Aroclor 1260 at 100 ppm had no effects on reproduction over two generations [228]. At higher dietary levels, reproductive effects Included poor mating performances, fewer litters, reduced litter size, and high postnatal death rates in the litters. In rabbits, Aroclors 1221 and 1254 were not fetotoxic when administered only during gestation in amounts equivalent to dietary levels of about 50-500 ppm ,[229]. However, when administered during gestation at higher levels (600-2,500 ppm dietary equivalent), Aroclor 1254 caused resorptions, abortions, maternal death, and, in two fetuses, asymmetric skulls [230]. Delaying administration of PCBs until after the first week of pregnancy did not eliminate the effects.
Feeding rhesus monkeys Aroclor 1248 at 25 ppm for 2 months resulted in a high degree of infertility that persisted for at least 8 months after
GENP 007021
121
775422
WATER PCB-SD0000056782
the last ingestion of PCBs [232]. In another experiment, rhesus monkeys
fed Aroclor 1248 at 2.5 and 5 ppm for 6 months had irregular menstrual
cycles with excessive and prolonged bleeding [233]. Even though these
monkeys conceived well on mating, resorptions and abortions were frequent,
and infertility was common in subsequent matings [233]. Nursing infants
developed chloracne-like signs within 2 months and infants frequently died
during the nursing period. The milk contained PCBs at 0.154-0.397 ppm
[234].
There are no reports of infertility or abortions attributed to
PCB consumption or exposure. There are reports of undesirable effects in
-
children born to mothers exposed to PCBs in the diet and of undesirable
t
effects developing from nursing such mothers.
''
Babies born from mothers with
Yusho
|
r
were often dark colored and ?
developed signs of Yusho after nursing [176,182,183]. In at least one
'
case, Yusho developed in a baby who was only exposed to PCBs by nursing
;
.*1T!
'
[182] . Concentrations of PCBs in milk were not determined at the time of
?
the Yusho poisoning. A milk sample obtained after birth of a normal baby
from a woman exposed to PCBs at work contained PCBs at 0.25 ppm, and
nursing was discontinued [195]. The woman's exposure history and time of
last exposure were not given, but PCBs were present in her blood at 24 ppb.
Based on the findings in monkeys [234] the decision to not nurse the baby
seems entirely justified.
775423
122
ENP 00702~>
WATER PCB-SD0000056783
TABLE III-9
EFFECTS OF PCBa ON HUMANS
PCB Intake
Source
Duration
Exposure Index
Environmental, Amount/kind
Blood (ppb)
Effects
Ref.
Ingestion Occupational
Vf ft ((
M M M ft
Up to 8 non 0.3-4g Kanechlor 400
>50
Yusho
145 185
Not known
10 mg/cu m
-
Unbearable
130
irritation
4-8 mon
5-7 mg/cu m Aroclor 1254
Chloracne, no liver injury
186
2.5-4 mon
Not reported
Chloracne, hyperpig mentation
187
<1-20 yr
0.2-1.6 mg/cu m Kanechlors
370, ave.
Chloracne, hyperpig mentation, liver inj ury
191
2.5 yr ave.
Not reported Kanechlors
820, ave.
Chloracne, no liver injury
194
Not reported >0.25 mg/cu m Not reported
130-520
Chloracne, liver injury
195
2.5-18. yr
0.013-0.27 mg/cu m Not reported
36-286
Irritation, liver inj ury
197
14 mon ave. It
0.1 mg/cu m Not reported
-
Not reported
<1-14
refuse workers
Chloracne, liver injury
No effects
190 199
GENP 007023
WATER PCB-SD0000056784
TABLE III-9 (CONTINUED)
EFFECTS OF PCBs ON HOMANS
PCB Intake
Source
Duration
Exposure Index
Environmental , Amount/kind
Blood (ppb)
Effects
Ref.
Occupational ft ft
2-23 yr 1-23 yr Up to 15 yr
0.32-1.44 mg/cu m Aroclor 1242
0.32-1.44 mg/cu m Aroclor 1242
Not reported Kanechlors
If Not reported Not reported Kanechlors
It
General environment
4 years Continuous
(>1 mg/cu m) Aroclor 1242
Air, 1-100 Food, 10-20 Mg/d
>200 <200
Chloracne, liver injury
196
No effects
196
7-300
24 10-100 74-1,900
Chloracne, elevated triglycerides
192, 193 -
Normal baby Mild chlor acne
195
No effects
198
>1-30
No effects
137 141
775425
124
GENP 007024
WATER PCB-SD0000056785
TABLE III-10 EFFECTS OF PCB INHALATION ON ANIMALS
Exposure Conditions
Material
mg/cu tn Duration
Species
Effects
Ref
Pydraul A 200 30,000
Solvol
10,000
tl 250-500
Decachlorodiphenyl
ft
2,500 800
ft 4 and 80 Aroclor 1242 8.6
11 6.8 ft 1.9Aroclor 1254 5.4 ' f 1.5
2 hr
Rats PCB in liver, 70 ppm
97
3 hr
It 1002 mortality, liver necrosis
202
8-69 3-hr exposures
ft
Liver necrosis, hyper 202 plasia of Kupffer cells
6 hr
ft Irritation, no gross effects
98
6 hr/d, 5 d/wk, 4 wk
ft
Irritation, increased
99
liver weights, micro
scopic liver changes
blood cell changes
ft ft No irritation,
99
increased liver
weights in females
7 hr/d, 5 d/wk, 3 wk
Mouse, None rat, cat t guinea
Pig, rabbit
203
7 hr/d,
tt tt
5 d/wk,
17 wk
203
7 hr/d, ft II 5 d/wk, 31 wk
203
7 hr/d, 5 d/wk, 17 wk
7 hr/d, 5 d/wk, 31 wk
tt Microscopic liver changes
li Microscopic liver changes; reversible
203 203
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TV. ENVIRONMENTAL DATA AND BIOLOGIC EVALUATION
Environmental Concentrations Two reports of workroom air concentrations of PCBs appeared in 1954
[186,190], Puccinelli [186] studied the concentrations in air of a capacitor factory in Italy, using the methods of Elkins [130], and found ~ concentrations in 500-liter air samples of 5.2-6.4 mg/cu m. Miegs et al [190] did not report on the analytical methods they used to determine concentrations of PCBs in the breathing zones of workers exposed when a heat exchange unit in a Connecticut factory leaked. From the description of the factory, it is likely that the exposures were largely to vapors; the concentration found was 0.1 mg/cu m.
In 1959, Elkins [130] reported that over a number of years, PCBs in some Massachusetts plants ranged up to 10.5 mg/cu m of air (Table TV-1).
TABLE IV-1 PCB CONCENTRATIONS MEASURED IN MASSACHUSETTS FACTORIES
Process
Capacitor Impregnating
It . It
Capacitor soldering Oil mixing Regulator filling Adapted from reference 130
PCB Concentrations (mg/cu m)
Maximum
Average
10.5 5.5 0.3
0.9 1.1 0.2
5.8 4.5 0.2
0.8 0.6 0.1
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Of 21 air samples collected in capacitor impregnating operations,
Elkins considered that hazardous concentrations (>1 ppm for Aroclor 1242;
>0.5 ppm for Aroclor 1254) existed in 15. while the sampling and
analytical methods used were not documented, Elkins [130] recommended
sampling with either a fritted bubbler or two impingers in series, both
containing amyl acetate, and analyzing by the sulfur lamp method.
Occupational environmental studies were conducted in five Japanese
plants by Hasegawa et al [191].
Kanechlors 200 (predominantly
dichlorobiphenyls), 300 (mostly trichlorobiphenyls), and 400 (mostly
tetrachlorobiphenyls) were used or manufactured in the plants. Air samples
were drawn through filter paper to collect particulate matter and normal
hexane to collect vapors and analyzed by GLC. The data are summarized in
Table III-7. In the paired samples, the vapor concentrations exceeded the
particulate concentrations. One of the plants was a biphenyl recovery
plant where PCBs were not used. In this plant, PCB concentrations were
<0.02 mg/cu m. In the PCB manufacturing plant, PCB vapor concentrations
were 0.026-0.163 mg/cu m, and particulate PCB concentrations were 0.019
0,037 mg/cu m. Higher PCB concentrations were found in the capacitor
plants: 0.095-0.965 mg/cu m of vapors, and 0.20-0.65 mg/cu m of
particulates. In one particulate sample collected in a capacitor plant
after a spill, the PCB concentration was 6.2 mg/cu m.
Staiff et al [243] in a 1974 report were concerned about emissions
from burned-out PCB-containing ballasts in fluorescent fixtures in their
laboratory. The investigators collected samples in two midget impingers,
containing ethylene glycol and connected in series. The samples were
analyzed by GLC. PCB concentrations in the air ranged from 0.012 to 0.166
'
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ng/cu m when the ballasts burned out and were 0.002 mg/cu m 3 days later. In a 1976 report of a survey of Australian workers exposed to Aroclor
1242, Ouw et al [196] listed breathing zone concentrations ranging from 0.32 to 2.22 mg/cu m before corrective measures were taken, and from 0.08 to 0.75 mg/cu m after installing improved ventilation. Breathing zone samples were collected at 30 liters/minute using Greenburg-Smith impingers containing 75 ml of isopropanol. The concentrations found are shown in Table IV-2.
TABLE IV-2
PCB CONCENTRATIONS IN THE AIR INSIDE A CAPACITOR PLANT BEFORE AND AFTER IMPROVEMENT OF EXHAUST voTILATION SYSTB1
Areas in the Impregnation Room
PCB Concentrations mg/cu m
Before
After
Area in the unloading tank in front of exhaust register from operator's breathing zone
Area in the unloading tank not in front of exhaust register
General atmosphere near tank
Soldering area
Adapted from reference 196
1.44
2.22 1.08 0.32
0.75
0.7 0.18 0.08
Exposures of electrical and materials technicians during 1976 to PCBs contained in materials they tested were evaluated by Levy et al [197]. Air samples were collected on magnesium silicate "Florisil" at 50 ml/minute for
128 775429
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4-8 hours and analyzed by GLC utilizing electron capture detection.
Breathing zone samples were collected on a single day from nine employees
for 8 hours. The concentrations in the nine breathing zone samples, which
would represent TWA exposure concentrations for the day, ranged from 0.014
to 0.073 mg/cu tn. Concentrations of PCBs in nine point source samples
collected over 4-8 hours on each of 3 days ranged from 0.013 to 0.264 mg/cu
m, and in 19 room air samples collected over 4 hours on each of 3 days,
from 0.08 to 0.16 mg/cu ra.
.
A plant manufacturing PCBs in the US was surveyed for worker exposure
in July 1976 [244] , Three Aroclors (1016, 1242, and 1254) were made in the
PCB production area. To begin the process, biphenyl and chlorine were
piped into a chlorinator with a catalyst and allowed to react. Two
separate groups of chlorinators were used, for Aroclors 1242 and 1254. The
product resulting from the reaction passed through a purifying operation,
or to a distillation column as in the case of converting Aroclor 1242 to
Aroclor 1016, and then on to the storage tanks. Mixing tanks were used to
give the desired properties to the final product.
Although the operation was outdoors and theoretically a closed
system, potential for employee exposure existed when samples were drawn or
leaks occurred. Local exhaust ventilation was used in two operations: (1)
while filling 55-gallon drums, hoses were placed near the openings, and (2)
when employees tested samples drawn from the chlorinators, their work
station was equipped with an exhaust fan and hood.
Eleven personal and seven area air samples were taken in the PCB
production area for 6-8 hours at a flow rate of 200 cc/minute [244] . PCBs
ware collected on Florisil, desorbed with hexane, and analyzed by GLC with
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EC detection. Aroclor 1016 was the PCB produced on the sampling dates, and it was used as the standard for quantitating airborne PCBs. Personal air sample concentrations of PCBs reported as Aroclor 1016 ranged from 20 to 86 Mg/cu m, while PCBs in area samples ranged from 16 to 55 yg/cu m. The data are presented in Table IV-3.
TABLE IV-3
PCB CONCENTRATIONS FOUND IN A PLANT MANUFACTURING PCBs ON 2 CONSECUTIVE DAYS Oig/cu m)*
Personal Air Samples Job Title
Premium operator Second operator Column operator Still operator Standard operator Distribution operator
7/21/76 47 46 64 40 54
7/22/76 20 43 51 86 61 36
Area Air Samples
Location
7/21/76
2/22/76
Drumming
43 51
Temperature testing
25
52
Chlorinators
55
36
Incinerator burner
16 -
Total sampling time varied from 409 to 455 minutes and sample volumes varied from 67.6 to 201.6 liters.
Adapted from reference 244
130
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Saco and Hasegava [32] studied concentrations of PCBs in factories
that had discontinued their use in production of pressure-sensitive copying
paper 2 years earlier. PCB concentrations in the factories had not been
determined when PCBs were being used, but were considered [3] to have been
similar to those found by Hasagawa et al [ 196] in capacitor manufacturing
plants. The concentrations found by Sato and Hasvgawa [32] at the time of
sampling ranged from 0.13 to 4.4 Mg/cu m. The PCB concentrations in the
outdoor air around the factories were 0.043-0.09 Mg/cu m [3],
Another study of contamination in factories after PCB use had been
discontinued was reported by Fujiwara et al [33]. These investigators
found 0.25 mg/cu m in air of a factory that had previously used PCBs in
silk glossing. In addition to air contamination, PCBs were found in the
dust around machinery and in the floor boards.
PCB concentrations found in the air of some other factories and their
surrounding environments in Japan were summarized in 1976 by Tatsukawa
[245].
Concentrations found before 1957 in a factory producing
transformers and capacitors ranged from 0.39 to 4.5 mg/cu m. The factory
was said to have been old-fashioned with bad ventilation [245] .
Concentrations found in warehouses for carbonless copying paper in 1972
ranged from 2 to 70 Mg/cu m. In the same year, concentrations of 0.04-0,05
Mg/cu m were found in a university laboratory where PCBs were used, and
concentrations of 0.006-0.12 Mg/cu m were found in areas of mills that
recycled paper. Background concentrations found in urban areas of Tokyo,
Osaka, and Matsuyama City were <0.002-0.04 Mg/cu.m.
Background concentrations of PCBs in ambient air over the US have
been reported in ng/cu m quantities [26,38] . Average concentrations of
007031
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about 100 ng/cu m were found in Florida and Colorado in 1975 [38].
Control of Exposure The present primary use of PCBs is as dielectric or Insulating fluids
for electrical capacitors and transformers. Potential hazards of PCBs in these industries result from inhalation and dermal exposures. It is here that engineering controls, such as local exhaust systems, are necessary.
Local exhaust systems should be designed and operated in conformance with American National Standard Z9.2-1971 Fundamentals Governing the Design and Operation of Local Exhaust Systems [246]. Guidelines for handling capacitor and transformer askarels Include the following recommendations from the American National Standards Institute (ANSI) [4]: (1) Enclosed systems of sealed piping, properly gasketed joints, valves, containers, and processing chambers should be used for any portion of the operation where askarel temperatures may exceed 55 C; (2) Enclosure should preferably extend to all other portions of the system insofar as practicable; (3) Operations utilizing PCBs should be isolated from other manufacturing areas to avoid cross contamination; (4) Provision should be made for adequate ventilation and regulation of manufacturing operations to avoid open exposure to askarels; (5) When askarels are used at elevated temperatures (especially 55 C or higher), engineering controls must be applied, either by the use of closed systems or by effective local exhaust ventilation with general workroom exhaust.
Durfee et al [247] cited the following potential sources of air emissions of PCBs in transformer and capacitor manufacturing operations: (1) vapor exhaust from stream jet ejectors; (2) evaporation from accidental
132 775433
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spills; (3) evaporation from hot surfaces as part of flood-filling,
inspection, or holding operations', evaporation from plant waste water.
(4) vacuum pump exhausts;
(5)
There are currently no commercially available fluids which can be
considered as totally acceptable substitutes for PCBs in the broad range of
AC capacitors, nor are there substitute dielectric systems which would
satisfy reliability and safety requirements in most applications [28].
Transformers containing PCBs represent only about 57. of the US transformer
market, and are used only where safety and reliability are of prime
importance. For new installations, building and installation design
provisions could be made to accommodate the use of filled, open dry-type,
or sealed dry-type transformers, Major construction changes would be
required to compensate for the fire resistance of askarel-filled ur._ rs if
existing askarel-filled transformers are to be replaced with oil-filled
units of equivalent electrical ratings [4],
Environmental Sampling and Analytical Methods (a) Air Sampling Before discussing the various methods available for sampling airborne
PCBs, it is pertinent to discuss the criteria for an ideal sampling device. NIOSH evaluated an industrial worker's exposure and found that sampling in the breathing zone gives a truer picture of actual exposure than does area sampling. The first criterion for an ideal air sampling device then is that it be amenable to personal sampling. In addition, it should be light, compact, and small enough so that workers can pursue their daily activities without being aware of its presence. The second criterion is that the
GENP 007033
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%
sampling device have a sufficient capacity for PCBs to enable the collection of an air sample representative of a typical workday. Thirdly, recovery of PCBs from the sampling device should be quantitative or, at the least, reproducible. Finally, the sample must be stable in or on the sampling device between the time of sampling and the time of analysis. " This latter criterion is hardly of concern here due to the general stability of PCBs.
An air sampling procedure using fritted bubblers or impingers filled with toluene was published by ANSI in 1974 [4]. Neither the sampler capacity nor the sampling efficiency had been experimentally evaluated. Where high sampling flow rates or high capacities were required, additional bubblers or impingers in series were recommended.
Bidleman and Olney [248] used porous polyurethane foam for collecting samples of atmospheric PCBs. They found that the polyurethane foam showed excellent collection efficiency (992 or better) for tri-, tetra-, and pentachlorobiphenyls. The authors [248] did not address the matter of 8ample recovery from the sorbent.
In an environment where carbonless copy paper was being used, Nishlyama et al [249] collected PCBs by drawing the air through a cooled column filled with Shimalite, a gas chromatographic solid support similar to Chromosorb W. The collection efficiency of the device was 952 and the PCBs were eluted from the column with hexane. Other investigators used 52 glycerol-coated Florisil for collecting organochlorine pesticides and PCBs from air [250]. Collection efficiencies were 90-1002 for PCBs.
Harvey and Steinhauer [251] collected ambient air samples of PCBs using 0.25% OV-17 silicone oil coated on ceramic saddles (distillation
i
134 775435
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column packing). The collection efficiency of this device was 70%. More recently, Gian et al [252] found that sorbent tubes packed with deactivated Florisil could be used for collecting PCBs and phthalates from air [252] . These compounds were found to be effectively retained by Florisil. The authors did not discuss efficiency of recovery.
In 1976, Laveskog and Lindskog [253] described a stack sampling device for chlorinated hydrocarbons which they used for PCB collection. This device utilized glass wool for the collection of particulates followed by a sorbent, 25-40% Apiezon M on Chromosorb W, to collect vapors. The collection efficiency of the column was 99%, and desorption efficiency with absolute ethanol was 87%. The authors investigated charcoal as a sorbent, but found it unsuitable for their purposes since the PCBs could only be recovered by extraction in a soxhlet apparatus with chloroform which in turn could not be used with electron capture detection.
Occupa:ional Safety and Health Administration (OSHA) workers have used charcoal tubes for personal air sampling for PCBs (RG Kupel, written communication, 1976). While the sampling device would be expected to have good capacity for PCBs, recovery from charcoal is not quantitative. Little other information is known about this method.
A NIOSH Standards Completion Program Report [254] indicated that PCBs with 54% chlorine content were effectively trapped on a fibrous glass filter. However, the presence of PCB vapor either apparently was not addressed or was assumed to be negligible. This may not be a valid assumption, particularly since another report from the same program [255] showed that PCBs with 42% chlorine content have appreciable vapor pressure.
GENP 007035
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NIOSH has also investigated the method of Giam et al [252] , using
Florisil as a sampling medium, in industrial environments. Florisil (30/48
mesh) was placed in a tube similar to that used in the charcoal tube method
for solvents, 100 mg in the front section and 50 mg in the back. The
retention capacity of this sampling device for PCBs was evaluated under
laboratory and field conditions, using various vapor generation techniques.
In laboratory experiments, PCBs at 10 yg/liter and 75% relative humidity
were sampled through a 100-mg Florisil bed at 0.2 liter/minute with no
evidence of breakthrough after 4 hours (48 liters). Of 21 samples
collected on Florisil in a capacitor plant, only 6 had PCBs on the backup
section and all 6 backup sections contained 1% or less of the total PCBs in
the tube. The volumes of air sampled ranged up to 61 liters, and PCB
concentrations in air as high as 1.5 jig/liter were measured. Other
laboratory experiments showed that PCBs could be desorbed quantitatively
from Florisil with hexane. Results from Florisil tube and lmpinger samples
taken side by side in the capacitor plant and analyzed with a single
commercial PCB product as a standard were statistically similar.
Impingers are not suitable for personal sampling and are inconvenient
to use because they must be recharged with the sampling solvent frequently
and must be used in series. The handling of absorber solutions is
difficult because of the potential for spillage and leakage of the solvent
and samples during transport to and from the sampling site. Solid sorbent
sampling devices are well suited for personal sampling since they are
relatively small, and personnel wearing the devices quickly become unaware
of their presence, enabling more representative sampling. Shipment of
these devices is relatively simple.
136
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Of Che solid sorbent sampling devices discussed, Florisil-filled Cubes are deemed the most advantageous because Florisil has a high capacity for PC3s and can be quantitatively desorbed; field evaluations have shown that Florisil-filled tubes are easier to handle and more convenient than impingers. Therefore, the Florisil-filled tube method is recommended for collection of PCBs from air, as detailed in Appendix I.
(b) Analytical The chemistry of PCBs was extensively reviewed by Hutzinger et al [ 1] , and PCB analytical chemistry has been reviewed by several authors [256-264] but only references pertinent to selection of an analytical method for determination of PCBs in industrial air samples will be discussed here. Of the analytical techniques available, the one most widely used for determining PCBs is GLC with EC detection. This technique is rapid, precise, and very sensitive. The far greater sensitivity of EC detection compared with that of the flame ionization detector (FID) is demonstrated by comparison of their relative responses to various PCB isomers, shown in Table IV-4 [ 1].
CjP.NP 007037
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775438 WATER PCB-SD0000056798
TABLE IV-4
RELATIVE MOLAR RESPONSES OF ELECTRON-CAPTURE AND FLAME-IONIZATION DETECTORS TO SOME PCBs
,iAM SanfcAluaS>la.l)ti M. *
Relative Molar Resoonse
PCB
Electron Capture
Flame Ionization
2-chloro 3-chloro 4-chloro 2,2'-dichloro 2,4-dichloro 2,6-dichloro 3,3'-dichloro 3,4-dichloro 4,4'-dichloro 2,4,4'-trichloro 2,2'4,4'-tetrachloro 2,2'6,6'-tetrachloro 3,3'4,4'-tetrachloro 3,3'5,5'-tetrachloro 2,3,4,5-tetrachloro 2,3,5,6-tetrachloro 2,2'4,4'6,6*-hexachloro 3,3'4,4'5,5'-hexachloro 2,2'3,4'5,5'6,6'-octachloro 2,2'3,3'5,5'6,6'-octachloro decachloro
Adapted from reference 1
1.00 0.20 1.10 5.16 . 17.7 32.0 6.10 15.2 5.97 135 106 20.6 396 320 367 259 347 726 1,180 1,150 1,410
.
1.00 0.92 0.87 0.99 0.86 0.91 0.94 0.86 0.81 0.78 0.87 0.90 0.87 0.85 0.87 0.71
1
1
4
During the GLC-EC detection analysis of PCBs, multicomponent mixtures
of various PCBs are almost always encountered. The samples analyzed may or
may not resemble a commercial PCB mixture. If so, the appropriate
commercial PCB mixture can be used as a standard for quantitation; if not,
a commercial mixture should not be used. Quantitation cannot be accurate
since it is baaed on incomplete resolution of PCB isomers. Even if
complete resolution were possible, all PCB isomers are not available for
standards and the specific EC detection response of each isomer would need
138
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co be known.
Many different methods have been used to "quantitate" or estimate
PC3s. Heights or areas of one [263], two [264], three [265], or more
[266,267], or of all chromatographic peaks [268-270] of a given sample have
been used for comparison with standard commercial PCB mixtures. The chief
disadvantage of such methods is that when the chromatogram of the sample
does not closely resemble that of the standard the estimates are neither
precise nor accurate. An improvement upon these methods is the use of
mixed PCB standards, as described by Beezhold and Stout [271]. This
procedure involves mixing various proportions of different PCB commercial
mixtures, such as Aroclor 1242 and Aroclor 1254, and obtaining sets of
chromatograms. The chromatogram most closely resembling the sample is
selected and the corresponding- mixture is used as the standard.
Sawyer [269], in a collaborative study, evaluated the quantitation of
PCBs in chicken fat. He found that the use of the total peak area or the
sum total of all peak heights gave better results than did the use of
selected peaks. The use of mixed standards gave good results when the
composition which best duplicated the response pattern of the sample was
used. This was adopted as an official method by the Association of
Official Analytical Chemists [272].
Using a different approach to standardization, Rote and Murphy [273]
produced a standard response curve using Aroclors 1232, 1242, 1248, 1254 ,
1260, and 1262.
This plot was of the total area responses on the GLC
trace divided by the weights of the Aroclors injected versus the average
number of chlorine atoms in the molecule. The peaks in each chromatogram
were identified as to chlorine content per chlorobiphenyl molecule, and
GENP 007039
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WATER PCB-SD0000056800
each sample could then be quantitated using the response curve. The
accuracy of this method is not greater than that of the methods previously
mentioned, since it has been shown that the response of EC detection varies
greatly with the degree of chlorine substitution and also with the relative
position of the chlorine substitution [1],
Risebrough at al [274] and Collins et al [268] used dichlorodiphenyl-
dichloroethylene (p,p'-DDE) as a standard and assumed that the response of
each chlorobiphenyl isomer was equal to that of p, p' -DDE. This method can
only be grossly approximate, since the response of EC detection to
individual PCB isomers varies greatly [1],
Risebrough et al [274] also reported the use of microcoulometric
detection to determine total chlorine content, using a commercial PCB
mixture as a standard. Sawyer [269] compared the EC detection with the
microcoulmetric and electrolytic conductivity detectors and found that the
latter two detectors are subject to more operational problems than is the
EC detection.
'
An analytical method utilizing a computer for the quantitation of
PCBa was described by Zobel [275] . This method would not be of value for
routine sample analysis in industrial hygiene laboratories because of the
expense or unavailability of a computer.
The method of Webb and McCall [276] involves standardization of an
Aroclor mixture whose peak-by-peak composition has been determined as
weight percentages of the total. Since the response-to-weight factor is
known for each peak, the actual weight equivalent of each peak in the
sample can be calculated despite vast differences of overall GLC patterns.
To utilize this method as a standard procedure, it is necessary that some
140 775441
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agency serve as a central repository for distribution of the reference materials. Presently, standards for Aroclors 1242, 1254, and 1260 as dilute solutions in iso-octane are available from Webb and McCall [276] . However, a fully characterized standard for the widely used Aroclor 1016 is not available. Potential future sources for these types of standards may be either the Association of Official Analytical Chemists or the US Food and Drug Administration. These organizations currently are interested in this method [277] and are planning to test it collaboratively.
The US Environmental Protection Agency has adopted the method of Webb and McCall [276] as a recommended procedure for quantitation of PCBs in industrial effluents [278]. Other investigators have also concluded that this method is the best available method of quantitation [279].
Berg et al [280] investigated the quantitation of PCBs in terms of derivatives. PCBs could be quantitatively converted by catalytic dechlorination to bicyclohexyl. However the authors [280] found that the relatively low level of sensitivity, because bicyclohexyl had to be determined by GLC with FID, was a marked disadvantage. They [280] found that treatment of PCBs with anitmony pentachloride under elevated temperatures and anhydrous conditions gave good yields (85%) of decachlorobiphenyl which could be determined by GLC with EC detection.
Armour [281] evaluated the perchlorination procedure of Berg et al [280] to determine its utility as a routine method for the confirmatory quantitation of PCBs. It was- found necessary to modify that procedure because of observed inconsistencies in the efficiency of conversion of Aroclors 1254 (90-100%) and 1242 (30-70%) to decachlorobiphenyl. Armour [281] attributed this to volatilization of the lower molecular weight PCB
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components during solvent evaporation before their reaction with antimony pentachloride. The remedy selected was to end evaporation while a small amount (0.1 ml) of solvent still remained, but this rendered the choice of solvents a more critical matter because of possible interferences during the perchlorination step. Chloroform was the solvent chosen because it minimized volatility and reacted favorably at the selected conditions. The Increased pressure produced as a result of this substitution of chloroform required discontinuing use of flame-sealed Carlus tubes as recommended by Berg at al [280] for containing the. elevated temperature-pressure perchlorination reaction. The recommended substitute was a vacuum hydrolysis tube having the same volume specifications (10 mm O.D. X 150 mm), a tight Teflon sealing valve, and a side venting arm [281].
Other modifications devised by Armour [281] included the addition of . methanol to the reaction mixture's extract to produce an azeotrope with the
residual chloroform which could then be evaporated to a small volume before dilution, preparatory to determination of decachlorobiphenyl. To determine the feasibility of a shortened reaction time. Armour et al tested iron as a catalyst, but decided that although a reaction time of 6 hours with iron catalyst resulted in quantitative (99% average conversion for six Aroclors) and reproducible (83rll0%) conversions, the catalytic modification offered little advantage over the overnight procedure.
Perchlorination has been used for the quantitation of PCBs by others [282,283]. While the sole perchlorination product was usually decachlorobiphenyl, there have been reports of undesired byproducts resulting from contamination of the antimony pentachloride with bromide ions [284,285]. Results of NIOSH investigations indicate that this
775443 142
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contamination problem can be eliminated bv vacuum distillation of the antimony pentachloride. Factors for converting decachlorobiphenyl to Aroclors are presented in Table IV-5.
TABLE IV-5 FACTORS TO CONVERT DECACHLOROBIPHENYL TO AN EQUIVALENT AMOUNT OF AROCLOR
Aroclor
Average Molecular
Weight
'
Q*
1221 1232
188.5 223
0.38 0.45
1242
. ' 257.5
0.52
1016
257.5
0.52
1248
292 0.59
1254
326.4
0.65
1260
361 0.72
1262
395.3
0.79
Calculated by dividing the average molecular weight by 499, the molecular weight of decachlorobiphenyl
Adapted from reference 281
From a review of the literature, NIOSH concludes that the simplest method of PCB quantitation involves standardization of samples with single commercial mixtures of PCBs. Should the composition of a sample not closely resemble that of a single commercial PCB mixture, the most accurate and precise method of quantitation available would be that of
143
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perchlorination, which seems Co offer Che besC approach for decermining
CoCal PCB content in samples when Che inicial concencradona of individual
PCBs are of liccle or no concern.
NIOSH recommends desorpCion of PCBs from Florisil wich hexane,
analysis by GLC, and quantitation of the sample by comparison with a
standard PCB mixture of similar composition (Appendix II). If a PCB
mixture with a composition similar to that of the sample is not available
as a standard, NIOSH recommends converting the sample PCBs to
decachlorobiphenyl for quantitation.
The methodology presented in Appendices I and II has been tested with
Aroclor 1016 in the laboratory and in practice. Operating parameters found
by NIOSH are presented in the Appendices.
Biologic Evaluation While there is presently no adequate method for biologically
monitoring industrial workers for exposure to PCBs, additional research may make feasible the routine measurement of residues of these compounds in blood or other body fluids.
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V. WORK PRACTICES
The employment of good work practices is required if hazardous occupational exposures to PCBs are to be prevented. The carcinogenic, teratogenic, dermatologic, and fetotoxic effects of PCBs largely determine the nature of necessary work practices.
(a) All locations where occupational exposure to PCBs occurs should be established as regulated areas and posted with signs warning persons of the procedures necessary upon entering or leaving.
When an otherwise closed PCB system is opened, eg, during the loading and unloading of storage tanks, the following work practices are desirable:
(1) Only authorized personnel should be permitted in the area; (2) Adequate ventilation should be provided and the exhaust air should not be discharged into any environment until it has been adequately decontaminated; (3) To prevent skin contact with PCBs, workers should be required to wear and use PCB-resistant protective clothing and equipment, including respirators. (4) Upon leaving regulated areas, workers should be required to remove such protective clothing and equipment and place it in impervious containers pending either decontamination or disposal; (5) After removing such protective clothing and equipment, workers should be required to wash their hands, forearms, and faces, and to shower after the last exposure of the day.
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WATER PCB-SD0000056806
Whenever a worker must come into direct contact with PCBs, eg, during cleanup of spills or maintenance of vessels, PCB-resistant protective clothing and an appropriate respirator must be worn.
(b) Leakage and Spill Procedures PCB spills are to be cleaned up promptly, either by the use of sorbent materials, such as sawdust, or by trapping and removal through pumping or other suitable means. In case of spillage of PCBs on clothing, the contaminated clothing should be removed as soon as practical, the skin should be thoroughly washed, and the clothing should be laundered or disposed of properly. Facilities and procedures for such cleanup must be provided at manufacturing facilities producing capacitors and transformers, because spills of PCBs are quite likely to occur during the filling and handling of such devices. Users of PCB-filled transformers should inspect them periodically for leakage. If leakage is found, the cause should be corrected and the spillage should be soaked up with sawdust or other absorbent material. The leak area should be cleaned finally with rags soaked with an appropriate safe solvent. Leaky transformer gaskets can be sealed temporarily by painting over the leaky area with epoxy cement. Refer to Transformer Askarel Inspection and Maintenance Guide [25], and Guidelines for Handling and Disposal of Capacitor and Transformer Grade Askarels Containing Polychlorinated Biphenyls [4] for further maintenance procedures. (c) Emergencies In emergencies, immediate measures must be taken to eliminate hazardous conditions. Non-essential workers must be evacuated until the emergency no longer exists. Any worker having visible contamination of the
146 775447
GENP 007046
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akin with PCBs must shower immediately unless other action is warranted. (d) Respiratory Protection To ensure against inadvertent exposure to PCBs, workers' respirators
must be properly selected, fitted, and maintained. A guide to industrial respiratory protection [286] has been developed which contains sufficient information to enable the establishment and maintenance of a respirator program that meets the requirements outlined in 29 CFR 1910.134. The guide [286] includes information on respirator selection, use, maintenance, and inspection, as well as a complete description of various types of respirators and their advantages and limitations, respirator fitting procedures, wearer training instructions, and physiologic and psychologic constraints on respirator use.
Several NIOSH studies [287-289] have shown that respiratory protection may be inadequate in many occupational situations, eg, abrasive blasting, coal mining, and paint spraying. For this reason, respirators are generally regarded by NIOSH as a type of control to be used only where engineering controls cannot be used, made adequate, or provided.
GENP 007047
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WATER PCB-SD0000056808
VI. DEVELOPMENT OF STANDARD
! I
Baals for Previous Standards
In 1942, the Subcommittee on Threshold Limits of the National
Conference of Governmental Industrial Hygienists compiled a list of maximum
permissible concentrations of atmospheric contaminants recommended by
various state industrial hygiene units [290], The eight states that made
recommendations for PCBs (chlorodiphenyls) were unanimous in recommending 1
mg/cu m. No basis for the recommendations was given.
Cook [291], in his 1945 listing of Maximum Allowable Concentrations
of Industrial Atmospheric Contaminants, cited PCB standards for California
and Utah of 1 mg/cu m and Oregon of 0.3 mg/cu m. He [291] also cited
unofficial guidelines for Massachusetts of 5 mg/cu m and for New York of 1
mg/cu m and he recommended 1 mg/cu m, based on the report of Drinker [132] .
The American Conference of Governmental Industrial Hygienists (ACGIH)
began listing PCBs (chloro di phenyl) with "toxic dusts, fumes and mists"
in its recommendations of maximum allowable concentrations of air
contaminants for 1946 [292]. It compiled its 1946 list from its 1942 list
[290] and from Cook's [291] list, and continued to recommend 1 mg/cu m for
PCBs.
The ACGIH continued to recommend 1 mg/cu m for PCBs (chlorodiphenyl)
until 1956 when it specified 1 mg/cu m as the limit for PCBs with 42%
chlorine and proposed a limit of 0.5 mg/cu m for PCBs with 54% chlorine
[293]. Each recommendation was clearly defined as a threshold limit value
(TLV) for an 8-hour TWA concentration to which it was "felt" workers could
be repeatedly exposed without adverse effect on their health.
148 775449
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In 1961, the ACGIH added the notation "skin" to the TLV of those substances, including PCBs, which in liquid form can penetrate the skin to cause systemic effects [294,295],
In 1962, the ACGIH published documentation of its TLV recommendations [296]. Based on information in the reports of Schwartz [123] , Drinker et al [125] , Meigs et al [190], and Treon et al [203], the ACGIH [296] concluded that for PCBs chlorinated to 42%, 1 mg/cu m would seem to offer reasonably good protection against severe systemic toxicity but may not guarantee complete freedom from chloracne. They also cited the information [207] that PCBs could be absorbed through the skin, causing fatty degeneration of the liver. In documenting its recommendation for PCBs containing 54% chlorine, the ACGIH [296] cited Drinker et al [125] , Drinker [132], and Treon et al [203] , and on the basis of these reports it [296] considered that 0.5 mg/cu m appeared to be reasonable for repeated occupational exposures.
The American Industrial Hygiene Association's Hygienic Guide "Chlorodiphenyls (containing 42% and 54% chlorine)" [297], published in 1965, adopted the ACGIH recommendations for time-weighted average exposures and suggested a short-expoBure tolerance for PCBs of 10 mg/cu m to prevent unbearable irritation, based on the report of Elkins [130]. The Hygienic Guide [297] provided information that minimum lethal doses applied to the skin of rabbits for 24 hours were 1 g/kg for PCBs containing 42% and 1.5 g/kg for PC3s containing 54% chlorine. It also recommended avoiding prolonged or repeated skin contact, and it recommended laundering of contaminated clothing before reuse, protecting the eyes from liquid splashes, treatment of the eyes if PCBs were splashed into them, and
GENP 007049
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' 775450
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periodic examinations to detect early evidence of skin irritation or liver damage.
In 1970, the International Labour Office published permissible levels of toxic substances for several nations [298]. The FCB standards for six nations are given in Table VI-1.
TABLE VI-1 PERMISSIBLE LEVELS OP PCBs FOR SIX NATIONS
Country
Standard (mg/cu m)
Type of Standard
Czechoslovakia 42% Chlorine 54% Chlorine
Finland' 42% Chlorine 54% Chlorine
Poland Romania
42% Chlorine 54% Chlorine USSR Yugoslavia 42% Chlorine 54% Chlorine
.
Adapted from reference 298
1.0 0.5
1.0 0.5 0.1
1.0 0.5 1.0
0.5 0.5
MAC " tv
MAC 8-hour tv
MAC Vt tv tv
tv
It
In 1975, Winell [299] compiled a list of international occupational hygienic standards for chemicals, including "chlorodiphenyl." She listed values for Sweden of 0.5 mg/cu m and for the German Democratic Republic of 1.0 mg/cu m. In both countries the standards were the same for PCBs containing 42% and 54% chlorine. The standards listed for the Federal Republic of Germany were 1.0 mg/cu m for PCBs containing 42% chlorine and
150
775451
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WATER PCB-SD0000056811
0.5 mg/cu m for those with 54% chlorine, respectively. The TLV documentations for PCBs published by the ACGTH in 1976 [300]
did not differ significantly from the original documentations [296] . However, the ACGIH [300] recalled, citing von Wedel et al [205] , that several deaths due to liver atrophy occurred among workers exposed to fumes of chlorobiphenyls and chloronaphthalenes, but pointed out that relatively few, if any reports had appeared of sytemic poisoning of workers exposed only to fumes of PCBs.
The ACGIH has retained a TWA of 1 mg/cu to as the TLV for PCBs with 42% chlorine content and a TWA of 0.5 mg/cu m as the TLV for those with 54% chlorine content (through 1976) [301]. However, a tentative short-term exposure limit (TLV-STEL) was added to the recommendations in 1976. STEL is defined by ACGIH [299] as the maximum concentration to which workers can be exposed for up to 15 minutes continuously without suffering from irritation , chronic or irreversible tissue change, or narcosis of sufficient degree to increase accident proneness, impair self-rescue, or materially reduce work efficiency. According to the ACGIH [301], the STEL is to be considered a maximum allowable concentration, or absolute ceiling not to be exceeded at any time during the 15-minute excursion period; such excursions are not to occur more than 4 times a day and there must be at least 60 minutes between them. The STEL recommended for PCBs was 1 mg/cu m regardless of the degree of chlorination. This recommendation was made on the basis that the TLV documentation for PCBs [300] suggested that the values should be ceilings never to be exceeded, rather than TWA values for 8 hours of exposure [301].
GENP 007051
WATER PCB-SD0000056812
The 1968 ACGIH recommendations [302], adopted as the federal standards for PCBs (29 CFR 1910.1000, Table G-l) are TWA 8-hour exposure concentrations of 1.0 mg/cu a for mixtures containing 42% chlorine and 0.5 mg/cu m for mixtures containing 54% chlorine.
Basis for the Recommended Standard
(a) Permissible Environmental Limit
The major.effects that have been found in workers exposed to PCBs are
chloracne [186-191,195,196], liver injury [190-193,196], and irritation of
akin and mucous membranes [192,196,197]. Exposures at peak PCB
concentrations of 5-10 mg/cu m have been reported as "unbearably -
irritating [130].
"I
Chloracne has been reported after occupational exposure to Aroclors
1242 [196] and 1254 [186], and to various Kanechlors [191,192,194,195], as
well as after ingestion of' Kanechlor 400 [146,153]. Chloracne has
frequently been associated with processes where the PCBs were heated [186
189,196]. The methodology in most of the exposure studies did hot
differentiate between vapor and particulate forms of the PCBs
[186,190,196]. In one study of Kanechlors in capacitor manufacturing
plants where chloracne was common, vapor (or small particulate)
concentrations (0.095-0.95 mg/cu m) exceeded particulate concentrations
(0.02-0.65 mg/cu m) [191]. In another capacitor plant where heated Aroclor
1254 was used, exposure concentrations were 5-7 mg/cu m, but the vapor
components were not seperately determined [186]. In this plant, chloracne
developed among workers after 4-8 months of exposure. A study of workers,
in a plant where the work situation indicated the exposures were to PCB
152
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vapors, showed chat chloracne developed after a minimum of 5 months and an average of 14 months of exposure [190], In this study, exposure concentrations of an undefined PCB were reported as 0.1 mg/cu m. In other studies where PCB concentrations were not measured, chloracne developed after 3-8 months of exposure [187,189].
These data show that chloracne can develop after prolonged exposures to PCBs in concentrations as low as 0.1 mg/cu ra, and that as the PCB exposure concentrations increase, the duration of exposure required for the development of chloracne decreases. The data also indicate that PCBs in the vapor phase may contribute substantially to development of chloracne. However, they do not prove that only PCB vapors cause chloracne. Particulate PCBs have been shown to be absorbed from inhaled air by experimental animals [97], and ingested PCBs have caused chloracne [ 146,153]. Occupational exposure to a variety of PCB mixtures (Aroclors 1242, and 1254, various Kanechlors, and others) has caused chloracne, and no commercial PCB mixture has been shown to have more or less chloracnegenic properties than others.
There are some studies of PCB workers in which chloracne was not found [197-199] . In one of these studies, the Aroclor 1242 concentrations were imprecisely reported [198] and in the others the PCB mixtures were undefined [199], The report by Levy et al [ 197] gave possible PCB exposure concentrations of 0.013-0.264 mg/cu m and breathing zone concentrations of 0.014-0.073 mg/cu m. Thus the data indicate that chloracne may be prevented by keeping PCB exposures below 0.1 mg/cu m (100 jig/cu m).
In some of the studies where chloracne developed, signs of liver injury were not found [186,194,195], but in the majority of studies where
GENP 007053
153
'
7?S4^
WATER PCB-SD0000056814
J't'fr '* rf f
(tg itiliM & 4 4 -#i
0u t*
chloracne was found, there were also indications of liver injury [190
193,196]. Evidence of Impaired liver function was found by other
investigators [197] in a study where workers had not developed chloracne.
Meigs et al [190] found evidence of slight liver injury in workers exposed
to PCBs at 0.1 mg/cu m, and Levy et al [197] found historical evidence of
liver injury in the medical records of workers in the plant where they
found exposures were <0.25 mg/cu m. Among the findings in these medical
records were elevated serum triglycerides [197].
Abnormal serum
triglycerides have been found in exposed workers by others [191-193], and
in the Japanese people who accidentally consumed PCBs [155,157,158,175,179
181]. The effect on serum triglycerides in workers was related to duration
of exposure [193] and, in the workers and in the Yusho patients, to
residual PCBs in the blood [175,180,193]. In the Japanese workers who were
removed from exposure, the effect remained for at least 2 years [193].
Other indications of liver injury in exposed workers included
occasional findings of elevated serum enzyme activities, and abnormalities
in various other liver function tests [190,191,196,197], A level of
exposure at which liver injury will not occur is not indicated by the
occupational exposure studies, since evidence of liver injury has been
found in the occupational studies with the lowest PCB concentrations. It
is not possible to determine whether liver injury occurred with exposures
at the lower levels of all the occupational exposure ranges reported, but
to protect workers from any liver injury it seems that exposures should be
maintained below 0.01 mg/cu m (10 jjg/cu m).
Animal experiments do not demonstrate a safe exposure level either.
Although Treon et al [203] found no evidence of liver inlurv in
775455 154
GENP 007054
WATER PCB-SD0000056815
experimental animals (rabbits, guinea pigs, cats, rats, and mice) exposed to Aroclor 1242 at concentrations of 1.9-8.6 mg/cu m for up to 31 weeks, Ouw et al [196] found evidence of liver injury in workers exposed to Aroclor 1242 at 0.32-1.44 mg/cu m. In their experiments with Aroclor 1254, Treon et al [203] found microscopic evidence of liver injury in animals exposed at 1.5 mg/cu for 31 weeks. Linder et al [228] found Increased liver weights in rats fed Aroclor 1254 at 1 ppm for two generations. The intake of PCBs at this dietary level can be compared to the intake from inhalation exposure at about 0.1-0.2 mg/cu m; thus, the animal experiments appear to confirm indications of liver injury in workers exposed to PCBs in this range. The combined studies of Levy et al [197], Meigs et al [190], Hasegawa et al [191], and Ouw et al [196], and the animal studies [203,228], provide further support to the conclusion that PCB exposures must be maintained at lower levels to prevent liver injury than to prevent chloracne.
Since indications of . liver injury can be found in reports of both occupational studies [190,191,196] and animal experiments [203,228] with the lowest PCB exposure, there is no proof of an exposure level that is adequately low to prevent liver injury.
The prevention-of liver injury is of particular concern because there is substantial evidence that arene oxides are formed during the metabolism of PCBs by animals [51,68,69,74,75,81,115,116,118], and the data offer no reason to suspect that humans metabolize PCBs differently from animals. PCB metabolites have been demonstrated to bind to nuclear components of hepatic cells of rhesus monkeys [51 ] and rats [81 ] and this is sufficient evidence to arouse suspicions that PCBs could be potential carcinogens in
GENP 007055
155
^J545(-
WATER PCB-SD0000056816
the workplace. Commercial PCB preparations that have been adequately
tested in rata [218,242] (Federal Register 42:6532-55, February 2, 1977)
and mice [221,240,241] have been demonstrated to cause liver tumors. No
liver tumors were found in rats fed Aroclors 1242, 1254, and 1260 at 1 ppm
is the diet, but each of these mixtures produced tumors at 10 ppm (Federal
Register 42:6532-55, February 2, 1977). In this same experiment a high
incidence of pituitary tumors was found in PCB-fed rats. In Yuaho patients
[160,161], and in American workers (written communications, HA Sinclaire,
June 1976; G Rousch, September 1976), preliminary studies only Indicate
that the occurrence of certain cancers may be excessive. However, the
findings in rata and mice demonstrate reproducible production of liver
tumors after ingestion of various PCB mixtures, and NIOSH concludes that
PCBs in workplace air are potential carcinogens.
Additional concerns for the health of workers and their families are
adverse reproductive effects [228,230,232,233], Including terata In animals
fed various PCBs (FL Earl et al, written communication, 1976), and adverse
effects in human and animal Infants nursed by PCB-exposed mothers
[101,182,233]. PCBs resembling those In maternal blood both qualitatively
and quantitatively have been found in human cord blood and in tissues of
newborn humans and Animals [101,138,139,168]. Fetal resorptions were
common, and dose related Incidences of terata were found in pups and
piglets when bitches and sows were fed Aroclor 1254 at 1 mg/kg/day or more.
Terata were not found in babies of Yusho patients (maximum consumption of
PCBs of about 0.15 mg/kg/day); however, many undesirable effects including
low birth weights and chloracne-like lesions at birth and after nursing
were found [176,182,183].
156
775457
GENP 007056
4
\
4 i
\
i;
1
4
I
A
w
WATER PCB-SD0000056817
Based on che findings of adverse reproductive effects, on its conclusion that PCBs are potential carcinogens in humans and on its conclusion that occupational and animal studies have not demonstrated a level of exposure that will not subject the worker to possible liver injury, NIOSH recommends that the TWA concentrations of PCBs in the breathing zone of workers be maintained at or below the minimally detectable TWA concentration for up to a 10-hour workday, 40-hour workweek. NIOSH considers the minimally detectable concentration of PCBs for the monitoring of occupational exposures to be 1 yg/cu m, based on its review of the literature and the methodology presented in Appendices I and II.
Maintenance of exposures to PCBs at or below this concentration should reduce risks of reproductive and carcinogenic effects, and protect the employees from metabolic dysfunction, hepatic injury, and dermal effects due to PCB exposures during their working lifetimes.
It is recognized that employees handling PCBs may have skin contact with these substances, potentially resulting in dermatologic and systemic effects . Consequently, appropriate work practices, training programs, and other measures should be required, regardless of the concentrations of airborne PCBs. Therefore, occupational exposure to PCBs has been defined as working with PCBs or with equipment containing PCBs that can become airborne or that can spill or splash on the skin or into the eyes, or the handling of any solid products that may result in exposure to PCBs by skin contact or by inhalation.
(b) Sampling and Analysis Based on an evaluation of the literature and on its own studies, NIOSH recommends sampling and analysis for PCBs as detailed in Appendices I
GENP 007057
157
. 775458
WATER PCB-SD0000056818
and II. Florisil haa been selected as the solid sorbent for PCBs because
it will collect vapors as well as particulates and PCBs can be
quantitatively recovered from it. The recommended Florisil sampling tubes
have been shown to have an adequate sorption capacity (at least 100 yg) for
monitoring occupational exposures at the recommended limit for up to a 10-
hour workday. NIOSH has used the sampling method for monitoring TWA
occupational exposures at 10-250 yg/cu m [197,244] by sampling at about 200
ml/minute for the entire workday. Total sample volumes of up to 100 liters
were collected. At 1 pig/cu m, 100 liters of air would contain 100 ng of
PCBs. The lower limit of PCB detection by GLC with EC detection was found
to be 32 pg/4-ptl injection. Since the contents of the Florisil tubes are
dissolved in 5 ml of solvent, this represents a total of 40 ng of adsorbed
PCBs. Although NIOSH recommends sampling at 200 ml/minute, it may be
feasible to use pumps that sample at faster rates if there are analytical
difficulties with samples of about 100 liters due to low concentrations of
PCBs.
(c) Medical Surveillance
Occupational exposure to PCBs has been shown to cause signs of liver
injury and impaired liver function. Ouw et al [196], Hasegawa et al [191],
and Levy et al [197] all found occasional incidents of elevated serum
enzymes: exposure conditions under which these will not occur are not
known.
Therefore, NIOSH recommends determination of SGOT and SGPT
initially and at annual intervals. The responsible physician may also wish
to determine serum triglyceride concentrations since these have been found
to be abnormal in some workers chronically exposed to PCBs [191-193,197].
Especially, elevated serum triglyceride concentrations have been found to
158 775459
GENP 007058
WATER PCB-SD0000056819
be related to duration of exposure and to the concentration of residual PCBs in the blood [193].
Although the data indicate that the recommended standard will prevent chloracne, it is not known that it will prevent other skin ailments. NIOSH recommends that in comprehensive physical examinations, special emphasis be given to the condition of the skin. & PCBs fed to bitches and sows have been found to be teratogenic (FL Earl et al, written communication, 1976). ..Although terata have not been observed in human babies whose mothers had been exposed to PCBs [ 176,182,183] , PCBs have been found in human embryos and fetuses [138,139,168], and undesirable effects (abnormal skin color and low birth weights) have been observed in neonates [176,182,183] born after their mothers had ingested PCBs. A woman who was occupationally exposed to PCBs had a blood PCB concentration of 25 ppb when her normal baby was born [ 195] . NIOSH considers that its recommended standard will protect unborn babies but recommends that women exposed to PCBs at work be advised of the potential hazards of PCB exposure to unborn children.
PCBs have been found in milk of women who have been exposed to PCBs [168,195] and babies have been adversely affected after being nursed by PCB-exposed mothers [182]. A safe level of PCBs in the milk of mothers occupationally exposed to PCBs is not known. Human milk samples in the general US population usually contain detectable amounts of PCBs, and about one-third of the whole milk samples have been found to contain >50 ppb and up to about 350 ppb (EP Savage, written communication, February 1977). It is not known if all the mothers from whom these samples were taken nursed their babies without effect. Infant monkeys who were nursed by mothers
GENP 007059
159
775460
WATER PCB-SD0000056820
in cheir milk at 150-350 ppb became sick and developed chloracne [234],
After consultation, the woman who was occupationally exposed to PCBs and
who had PCBs in her milk at about 250 ppb, stopped nursing her baby out of
concern for its health [195], Based on these considerations, NIOSH
recommends that women working with PCBs be counseled concerning the
advisability of nursing their babies.
(d) Personal Protective Equipment and Clothing
PCBs applied to the skin or cornea of experimental animals have been
shown to cause local lesions and liver and kidney injuries [205-208,225].
One worker who developed chloracne after 3 months of exposure to PCBs was
described as having frequently immersed his hands in the PCB mixture and
his clothes were described as often being impregnated with PCBs [189],
Employees working with an askarel containing 60% Aroclor 1254 frequently
developed skin rashes which were considered by the company physician to be
allergic or contact dermatitis from the askarel (In the Matter of General
Electric Company, File No. 2833, New York State Department of Environmental
Conservation, 1975). Other complaints of these workers that were ascribed
to the askarel included irritation of the eyes, nose and throat. Levy et
al [197] and Ouw et al [196] found that employees exposed to PCBs at 0.013
0.264 mg/cu m and 0.32-1.44 mg/cu m, respectively, complained of similar
irritations and, on examination, there were findings of skin rashes and
nasal irritation. Ouw et al [196] considered that one reason the blood PCB
concentrations in workers they studied did not decline (after improvements
in the ventilation system had reduced the environmental concentrations of
PCBs) was because the workers did not comply with the recommendations for
protecting their skin from PCB contact. 160
775461
GENP 007060
WATER PCB-SD0000056821
Based on ehese reports [189,196,197,205-208,225], NIOSH recommends
that employees working in situations where skin contact may occur be
provided with clothing that is impervious to PCBs and that will cover all
body surfaces where contact may occur. To prevent splashing PCBs into the
eyes, NIOSH recommends that employees wear appropriate goggles or safety
glasses in accordance with 29 CFR 1910.133 and ANSI Z87.1-1968. Since
NIOSH has found PCBs to be potential carcinogens and recommends that
exposures be maintained at or below 1 yg/cu m, it considers that only a
self-contained breathing apparatus with a full facepiece operated in the
positive-pressure mode will provide adequate protection when workers are in
areas where higher concentrations exist. Based on NIOSH studies [287-289],
other respiratory protective devices are not considered adequate to provide
the needed protection.
.
(e) Other Considerations
Engineering controls are recommended to maintain PCBs in closed
systems to reduce exposures to the extent feasible. Such a recommendation
is consistent with the Toxic Substances Control Act (Public Law 94-469) and
with the need to protect employees from exposure to PCBs. However, there
are situations, such as in accidental leakage from closed systems and in
repair of equipment, when PCBs may not be confined. The recommended
standard prescribes general work practices for PCBs as well as emergency
work practices. Employees should be informed of the hazards of working
with PCBs, and trained in the recommended general work practices and the
procedures to follow in emergencies. The-advantages to their health of
complying with the work practices and medical monitoring requirements of
the recommended standard should be explained to the employees. As Ouw et
GENP 007061
161
.
775462
WATER PCB-SD0000056822
al [196] pointed out, improving air quality does not go far in alleviating the workers' body burdens of PCBs without their cooperation in implementing the recommendations for protecting their skin from PCB contact.
NIOSH also recommends certain sanitation practices to minimize intake of PCBs by employees. Among these practices is the requirement that employees be provided with clean work clothing daily and that they change clothing before leaving work. The importance of this measure to the employee and the employee's family is exemplified in finding up to 180 ppm of PCBs in the dust of PCB-workers' homes [36]. PCBs may remain in contaminated premises for years [33]. Partly for the same reason, and because PCBs in contact with the skin can be irritating [196,197] and also because they have caused systemic effects in experimental animals [205-- 208,225], NIOSH recommends that workers shower before leaving work.
Toxic effects from ingestion of PCBs have been well documented in humans [145-185] and experimental animals [101,209-224,226-237,240-248]. Workers may have an intake of PCBs from their normal diet of 10-20 pg/day [46], and the maximum additional Intake expected from NIOSH'a recommended allowable work exposures might be of the order of 10 fig. NIOSH recommends that workers wash their hands before eating and that food, drinks, and smoking materials not be permitted in PCB work areas. The importance of this recommendation may be evaluated by considering that one drop of PCBs spilled on food, in drinks, or otherwise conveyed into the mouth may contain about 50 fig of PCBs, compared to a total intake of 20-30 fig from other sources, including allowable occupational exposures.
Because the consequences of working with PCBs may be substantial, NIOSH recommends that entry into PCB work areas be restricted to authorized
162 775463
GENP 007062
WATER PCB-SD0000056823
employees whose entry is logged daily, and whose exposures are monitored at least annually to ensure that airborne exposures are at or below the recommended TWA limit.
163
775464
GENP 007063
WATER PCB-SD0000056824
VII. RESEARCH NEEDS
There is a clear need for information in the following areas: (a) The effects of chronic exposure of animals and humans to PCBs at low concentrations require investigation. Epidemiologic studies of occupational groups and information on concentrations of PCBs in workroom air and any related clinical findings would be useful. (b) Chronic exposures of animals to PCBs at concentrations in the range of the recommended environmental limit. (c) Studies of the reproductive histories of women who have been exposed to PCBs in their occupational environments, including studies of status and development of Infants bom to these women. (d) The absorption efficiencies of various PCB mixtures by the dermal and respiratory routes. (e) The method of transport of PCBs in the blood and the partition between blood on the one hand, and fat stores and milk on the other. (f) A problem that confounds our understanding of the toxicity of PCBs is that of the toxic activity of contaminants associated with PCBs. The contaminants found in commercially important PCB products should be identified, prepared in pure form and studied toxicologlcally both as individual substances and as mixtures with other, related compounds. (g) Studies regarding methods of removing PCBs from the skin (cleansing). (h) Studies on the use of various barrier creams as a means of minimizing dermal exposure to PCBs.
164 775465 GENPnn~^, , WATER PCB-SD0000056825
(i) There is uncertainty regarding baseline values for PCBs in the blood of humans; research should be conducted to determine baseline values for the general population and for non-exposed industrial populations.
165 775466
GENP 007065
WATER PCB-SD0000056826
VIII. REFERENCES
1. Hutzinger 0, Safe S, Zitko V: The Chemistry of PCBs. Cleveland, The
Chemical Rubber Co Press, 1974, pp 3,4,7-9,22,23,197-220,243-48
.2 Mieure JP, Hicks 0, Kaley RG, Saeger VW: Characterization of
Polychlorinated Biphenyls, in Proceedings of the National Conference on Polychlorinated Biphenyls, November 19-21, 1975, Chicago, EPA6* 560/6-75-004. US Environmental Protection Agency, Office of Toxic Substances, 1976, pp 84-93
3. Kuratsune M (ed): Environmental Health Criteria for Polychlorinated Bi- and Terphenyls--WHO Environmental Health Criteria Programme (Japanese document to World Health Organization). Fukuoka, Japan, Public Health Association, Japan Environmental Agency, 1974, 159 pp
4. American National Standard: Guidelines for Handling and Disposal of Capacitor- and Transformer-Grade Askarels Containing Polychlorinated Biphenyls, ANSI C107.1-1974. New York, American National Standards Institute Inc, 1974, 35 pp
5. Leardini T: The properties of askarels and recommendations for their use in electrical equipment. Study Committee No 15, Working Group 02, Cigre' No. 35:11-31, 1974
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276. Webb RG, McCall AC: Quantitative PCS standards for electron capture gas chromatography. J Chromatogr Sci 11:366-73, 1973
277. Burke JA: Report on chlorinated pesticides. J Assoc Off Anal Chem 59:338-40, 1976
t 278.
Method for Polychlorinated Biphenyls (PCBs) in Industrial Effluents. Cincinnati, Environmental Protection Agency, Environmental Monitoring Support Laboratory, 1976, 40 pp
279.
Chau AST, Sampson RCJ: Electron capture chromatographic methodology for the quantitation of polychlorinated biphenyls--Survey and compromise. Environ Lett 8:89-101, 1975
280.
Berg OW, Diosady PL, Rees GAV: Column chromatographic separation of polychlorinated biphenyls from chlorinated hydrocarbon pesticides, and their subsequent gas chromatographic quantitation in terms of derivatives. Bull Environ Contam Toxicol 7:338-47, 1972
281.
Armour JA: Quantitative perchlorinatibn of polychlorinated biphenyls as a method for confirmatory residue measurement and identification. J Assoc Off Anal Chem 56:987-93, 1973
282.
Hutzinger 0, Safe S, Zitko V: Analysis of chlorinated aromatic hydrocarbons by exhaustive chlorination--"Qualitative and structural aspects of the perchloro-derivatives of biphenyl, naphthalene, terphenyl, dibenzofuran, dibenzodioxin and DDE. Int J Environ Anal Chem 2:95-106, 1972
283.
Mizutani T, Matsumoto M: Determination of polychlorinated biphenyls by an exhaustive chlorination method. Shokuhln Eiselgaku Zasshl 13:398-404, 1972 (Abst.)
284. Huckins JN, Swanson JE, Stalling DL:
Perchlorination of
polychlorinated biphenyls. J Assoc Off Anal Chem 57: 416-17, 1974
285.
Trotter WJ, Young SJV: Limitation on the use of antimony pentachlorlde for perchlorination of polychlorinated biphenyls. J Assoc Off Anal Chem 58:466-68, 1975
286.
Pritchard JA: A Guide to Industrial Respiratory Protection, No. NIOSH 76-189. Cincinnati, US Dept Health, Education, and Welfare, Public Health Service, Center for Disease Control, National Institute for Occupational Safety and Health, 1976, 150 pp
. 775489 188
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287.
Blair A: Abrasive Blasting Respiratory Protective Practices, No. NIOSH 74-104. Cincinnati, US Dept Health, Education, and Welfare,
Public Health Service, Center for Disease Control, National Institute for Occupational Safety and Health, 1974, 116 pp
288.
Harris HE: Coal Mine Dust Respiratory Protective Devices, Final Report Prepared by the Eastern Associated Coal Corporation for NIOSH Contract No. CPE 70-127. Cincinnati, US Dept Health, Education, and Welfare, Public Health Service, Center for Disease Control, National Institute for Occupational Safety and Health, 1974, 221 pp
289.
Toney CR, Barnhart WL: Performance Evaluation of Respiratory Protective Equipment Used in Paint Spraying Operations, NIOSH No. 76-177. Cincinnati, US Dept Health, Education, and Welfare, Public Health Service, Center for Disease Control, National Institute for Occupational Safety and Health, 1976, 110 pp
290.
National Conference of Governmental Industrial Hygienists: Report of the Subcommittee on Threshold Limits, in Transactions of the 5th Annual Meeting, NCGIH, Washington, April 9, 10, 1942, pp 163,164
291. Cook WA: Maximum allowable concentrations of industrial atmospheric contaminants. Ind Med 14:936-46, 1945
292.
American Conference of Governmental Industrial Hygienists: Report of the Sub Committee on Threshold Limits, in Proceedings of the 8th Annual Meeting, ACGIH, Chicago, April 7-13, 1946, pp 54-56
293.
American Conference of Governmental Industrial Hygienists: Report of the Committee on Threshold Limits, in Transactions of the 18th Annual Meeting, ACGIH, Philadelphia, April 21-24, 1956, pp 70,72,73,76,78
294.
American Conference of Governmental Industrial Hygienists: Report of Committee on Threshold Limits, in Transactions of the 23rd Annual Meeting, ACGIH, Detroit, April 9-12, 1961, pp 120-22
295.
American Conference of Governmental Industrial Hygienists: Threshold Limit Values for 1961, Adopted at the 23rd Annual Meeting, ACGIH, Detroit, April 9-12, 1961. Cincinnati, ACGIH, 1961, p 8
296.
American Conference of Governmental Industrial Hygienists, Committee on Threshold Limit Values: Documentation of Threshold Limit Values, ed 1. Cincinnati, ACGIH, 1962, pp 26,27
297. Chlorodiphenyls (containing 42% and 54% chlorine), in Hygienic Guide Series. Am Ind Hyg Assoc J 26 :92-94, 1965
298.
Permissible levels of Toxic Substances in the Working Environment-- 6th Session of the Joint ILO/WHO Committee on Occupational Health, Geneva, June 4-10, 1968, Occupational Safety and Health Series No. 20. Geneva, International Labour Office, 1970, pp 182-87, 197,204,223,231,331,346
189 775490
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299. Winell M: An international comparison of hygienic standards for chemicals in the work environment. Ambio 4:34-36, 1975
300.
American
Conference of Governmental Industrial Hygienists:
Documentation of the Threshold Limits of Substances in Workroom Air,
ed 3. Cincinnati, ACGIH, 3rd printing 1976, pp 51,52
301.
American Conference of Governmental Industrial Hygienists: Report of the ACGIH Committee on Threshold Limits for the Air of Workplaces, in Transactions of the 38th Annual Meeting, ACGIH, Atlanta, May 17-21, 1976, pp 27,28,30-36,158-60,164,184
302.
American Conference of Governmental Industrial Hygienists: Threshold Limit Values for 1968--Recommended and Intended Values, Adopted at the 30th Annual Meeting, ACGIH, St. Louis, May 13, 1968, pp 1,3,5,7
775491 190
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IX. APPENDIX I
SAMPLING PROCEDURE.FOR COLLECTION OF POLYCHLORINATED BIPHENYLS
General Requirements
(a) Air samples representative of the breathing tone, of vorher,
must be collected to determine the exposure from each Job or fro. the specific operation in each work area.
(b) Suggested records:
(1) Date and time of sample collection; (2) Pump model and serial number;
(3) Sample tube type and number;
(4) Sampling duration; (5) Total sample volume;
(6) Location of sampling;
(7) Temperature, pressure, and relative humidity at time of
sampling;
(8) Other pertinent information.
Calibration Since the accuracy of environmental sampling can be no greater than
the accuracy of the air volume measurement, the accurate calibration of the sampling pump is essential to the correct estimation of the volume of the sample that is collected. The required frequency of calibration is dependent on the use, care, and handling to which the pump is subjected. Pumps should be calibrated initially and recalibrated if misused or
191 775492
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repaired. L pumps receive hard usage, more frequent calibration may be necessary. Regardless of use, maintenance and calibration should be performed on a regular schedule and records of these should be kept.
The accuracy of calibration depends on the type of instrument used as a reference. The choice of calibration instrument will depend largely upon where the calibration is to be performed. Ordinarily, pumps should be calibrated in the laboratory. For laboratory testing, primary standards, such as a spirometer or a soapbubble meter, are recommended, although other standard calibration Instruments, such as a wet-test meter or dry gas meter, can be used. The calibration setups will be similar for all Instruments.
Instructions for calibration with the soapbubble meter follow. If another calibration device is selected, equivalent procedures should be used. Since thezflowrate of a pump depends on the pressure drop across the sampling device, in this case a "Florisil" tube, the pump must be calibrated while operating with a representative tube in line. The calibration system should be assembled in series following this order: soapbubble meter, water manometer, Florisil tube, and pump.
(a) Check the voltage of the pump battery with a voltmeter to ensure adequate voltage for calibration, and change or charge the battery if necessary.
(b) Turn on the pump and moisten the inside of the soapbubble meter by Immersing the buret in the soap solution and drawing bubbles up the inside until they travel the entire buret length without bursting.
(c) Adjust the pump rotameter to provide the desired flowrate.
775493 192
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(d) Check the water manometer to ensure that the pressure drop across the sampling train does not exceed 2.5 inches of water at 0.2 liter/minute.
(e) Start a soapbubble up the buret and measure with a stopwatch the time required for it to move between calibration marks.
(f) Repeat procedure (e) at least twice, average the results, and calculate the flowrate from the volume between the preselected marks divided by the time required for the soapbubble to traverse the distance.
(g) Record the volume measured, elapsed time, pressure drop, air temperature, atmospheric pressure, serial number of pump, date, time, and name of person performing the calibration.
(h) The rotameter reading should be corrected for temperature and pressure, if necessary.
Sampling (a) Samples should be collected as near as practicable to the
faces of workers without interfering with freedom of movement. (b) Samples should be collected to permit determination of TWA
exposures for every job involving exposure to PCBs and in sufficient numbers to express the variability of the exposures in the work situation.
(c) Apparatus for Breathing Zone Sampling (1) Pump, battery-operated, with clip for attachment to the
worker's clothing. Airflow through the pump should be controlled within 5% of the desired rate during the entire sampling period.
(2) Sorbent Tubes Glass tubes at least 7 cm long with 4 mm I.D, and containing
193 775494
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two sections of 30/48 mesh deactivated Florisil. (Florisil, 30/60 mesh, is
sieved to the proper mesh size.) The front section, preceded by a glass
wool plug, contains 100 mg adsorbent, and the backup section contains 50
mg. A urethane foam plug is placed between these sections and also behind
the backup section. The ends of the tube are flame-sealed to prevent
contamination before use.
Deactivate the Florisil before packing the tubes by drying a weighed
amount at 105 C for 45 minutes. After cooling to room temperature, add the
Florisil to a round bottom flask which can be attached to a rotary
evaporator. Add water at 3 ml/100 g of Florisil (ie, 37. W/W water) and
turn the mixture in the rotary evaporator for 1 hour or until it is
uniformly mixed (free-flowing).
(d) Collection and Shipping of Samples
(1) Immediately before sampling, break each end of the
sorbent tube to provide an opening at least one-half the Internal diameter
of the tube (2 mm).
.
(2) The smaller, or backup, section of Florisil should be
positioned nearest the sampling pump.
(3) The sorbent tube must be vertical during sampling.
Tubes should not be placed in a horizontal position since this may lead to
"channeling" of the sorbent bed.
(4) Do not pass air being sampled through any hose or
tubing before it enters the tube.
(5) Collect the air sample at a flow rate of 200 cc/minute
or less to obtain the total sample volume required. The recommended
maximum sampling volume for this method is 50 liters.
i ; i ,
`
'
I 1
i
i
,
194 775495
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(6) Cap che sorbent tubes with inert plastic caps immediately after sampling. Under no circumstances are rubber caps to be used. Label tubes and note precise location assignments.
(7) Handle one additional tube in the same manner as the
sample tubes except that no air is to be drawn through it. Label this tube
as a blank.
(8) If the tubes are to be shipped, pack them tightly to
minimize breakage in transit.
(9) Do not subject the tubes to extremes of temperatures or
to low pressures. (10)
Provide bulk samples of the PCB preparation whose
presence in the environment is suspected to the analytical laboratory. Do
not transport these bulk materials in the (same container as the samples or
blank tubes. If possible, also provide a bulk air sample to use for
qualitative identification.
195 775496
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X. APPENDIX II
ANALYTICAL METHOD FOR POLYCHLORINATED BIPHENYLS
Principle of the Method A known volume of air is drawn through a tube containing Florisil to
adsorb the PCBs present in the air sample. The collected PCBs are desorbed with hexane, and the resulting solutions are analyzed using gas-liquid chromatography with electron capture detection. The concentration of PCBs relative to a standard PCB preparation is read from a standard curve. If the air sample is found to differ significantly in composition from available PCB standards, then use . the alternate procedure of perchlorination described in paragraph (b)7 of Procedure.
Range and Sensitivity of the Standard Analysis NIOSH has found with Aroclor 1016, that the minimum detectable amount
of PCB is 32 pg/4 til. With a total desorption volume were 5 ml, this would represent a total sample of 40 ng of Aroclor 1016. Thus the method is capable of detecting a concentration of 40 ng in a 1 cu m air sample, or a concentration of about 1 tig/cu o in an air sample of 50 liters; The upper range of the analytical method is apparently limitless depending only upon the degree of dilution needed to maintain the concentration of the sample within the linear range of the electron capture detector (32 pg to 3 ng/injection). In practice, concentrations in workplace air have been found to be as high as 1.5 mg/cu m.
775497 196
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Interferences (a) Strict measures to avoid contamination are required when using
the electron capture detector. Foremost, the syringe must be thoroughly cleaned after each injection. Hexane to be used in the analytical procedure should be periodically analyzed by GLC for purity. It should " show no chromatographic peaks later than 45 seconds, if less than 5 nl have been injected.
(b) Any compound which has nearly the same retention time on the GLC column as one of the PCBs is an interferent. . This type of interference can often be overcome by changing the GLC operating conditions or by selecting another column. Retention time data on a single column, or even on a number of columns, cannot be considered as proof of chemical identity. It is important, therefore, that a sample of the bulk mixture of PCBs be analyzed at the same time as the contents of the sample tubes so that chemical identification of possible interferences can be made.
(c) The interferences which have been reported in the literature in the GLC analysis of PCBs are not expected to be important for this method. Chlorinated pesticides, such as DDT, DDE, etc, have been reported as interferences due to coextraction with PCBs during workup of samples such as water, tissue, soil, or biologic fluids. In the case of personal air sampling in an industrial environment, these interferences would not be present in amounts that would significantly interfere unless they were manufactured in the same area. Thus, unless these chlorinated pesticides are specifically known as potential interferents, extra cleanup or separation steps for these materials are not necessary.
197 775498
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(d) Sulfur-containing compound* in petroleum product* have been reported as interferences.
(e) If present in the PC3 mixture, biphenyl vill be an interference when samples are analyzed by perchlorlnatlon; however, PCBs for Che purpose of this recommended standard include biphenyl. ~ (f) Brominated Impurities in antimony pentachloride have also been found to lead to interferences in perchlorlnatlon procedures. Results from NIOSH laboratories indicate, however, that these brominated impurities may be removed by^vacuum distillation of the antimony pentachloride.
Precision and Accuracy The performance characteristics of the method as found by NIOSH are
presented below. (a) The volume of air sampled can be measured to 1Z if a pump
with a calibrated volume indicator is used. Volumes calculated from initial flow rate settings may be less accurate (5Z) because of changes in flow race during sampling.
(b) At airborne PCB concentrations of up to 10 mg/cu a, the front section of the Ilorisll tube has a 100Z collection efficiency for 50-liter air samples.
(c) Recovery of known amounts of PCBa adsorbed on Florinil is
quantitative (100%).
(d) Sealed tubes or desorbed sample solutions can be stored for 2 months without PCB loss.
(a) The precision of the analysis is dependent upon the precision and sensitivity of the technique used to quantitate the GLC peaks of the
198 GENP 007098
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samples and standards. The precision of the standard analytical procedure
has a relative standard deviation of 4.4%.
(f) The average conversion of PCBs to decachlorobiphenyl is about
100% with a relative standard deviation of about 2%.
(g) Recovery of decachlorobiphenyl subjected to the
decachlorination procedure is >99% with a relative standard deviation of
1.8%.
.
(h) The accuracy of these procedures is not known; accuracy
depends on the ability to separate and identify each compound in the PCB
mixture and to compare each with a known standard. Many of the isomers in
commercial PCB mixtures have not been separated or identified, and
standards for many of the isomers are not available.
Advantages of the Sampling and Analytical Methods
(a) The sampling , device is small, portable, and involves no
liquids,
(b) The capacity of the solid sorbent sampling device for PCBs is
large and recovery of PCBs from the sorbent is quantitative.
(c) The contents of the sample collection tubes are analyzed by
means of a rapid Instrumental method.
(d) Interferences are minimal, and most of those which do occur
can be eliminated by altering chromatographic conditions.
(e) The perchlorination
procedure provides qualitative
confirmation and quantitative measure of PCBs, since it is based on
measurement of the single GLC-EC detection response of decachlorobiphenyl.
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Disadvantages of the Sampling and Analytical Methods (a) The precision of the sampling method is limited by the
reproducibility of the pressure drop across the tubes. Pressure drop changes will result in variability in the flow rate and cause the sampling volume to be Imprecisely known because the pump is usually calibrated for iOnly one tube.
(b) A substantial difference between the composition of PCBs in the air sample and that of the commercial PCB mixture being used as a standard will result in a large error in accuracy when the standard analytical procedure is used, since estimation of the PCB content of the sample is based on comparison with such a PCB mixture.
Apparatus
(a) Gas liquid chromatograph equipped with an electron capture
detector capable of maintaining a detector temperature of 350 C.
(b) Glass column (6 feet x 2 mm I.D.) packed with 1.52 0V-17/1.952
QF-1 on 80/100 mesh Supelcoport.
(c) Vials (20-ml), with aluminum-lined caps.
<d) Microliter syringe (10-yl).
(e) Volumetric flasks (10-ml for standards) with glass stoppers.
(f) Method for determining peak areas. <*> Culture tubes, 13 x 100 mm, with unlined screw top caps. (h) Oven, capable of maintaining 160 C t 5 C.
<i) Sand bath. (j> Vortex mixer.
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GENP 007100
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Reagents (a) (b) (c) (d) (e) (f) (g)
Hexane, pesticide-grade quality, Nitrogen carrier gas, prepurified. PCB mixture under study. Antimony pentachloride, distilled under vacuum. Decachlorobiphenyl. Sodium sulfate, anhydrous. Hydrochloric acid, 20% aqueous.
Calibration and Standards
(a) Standardization Procedure
Use the particular PCB mixture as the standard that was being used in
the work area in which air samples were taken. Prepare standards in hexane
at concentrations ranging from 8 to 500 ng/ml. Calibration curves should
be established daily since the electron capture detector response may vary
from day to day. Plot the standard curve in terms of concentration (ng/ml)
versus area. Since the injection volumes of the standard and the sample
are identical, the concentration of the sample can be read directly from
the standard curve.
(b) Alternate Standardization Procedure (Perchlorination)
The product of the perchlorination of the PCB mixture with antimony
pentachloride is decachlorobiphenyl. Standards of decachlorobiphenyl are
prepared in hexane at concentrations ranging from 70 to
ng/yl.
Calibration curves are established daily since the electron capture
detector response may vary from day to day. The standard curve is plotted
in terms of concentration (ng/ml) versus peak area. Since the injection
201 ' 775502
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volume of the standard and the sample are Identical, the concentration of the sample can be read directly from this curve.
Procedure
(a) Cleaning of Equipment
All glassware used for the laboratory analysis should be washed with
a detergent, throughly rinsed with tap water, distilled water, pesticide-
grade acetone, and finally pesticide-grade hexane and then dried.
(b) Analysis of Samples
(1) Preparation of Samples
Score each tube witha file and place the glass wool and front
section in a clean, dry vial. Place theseparating urethane foam plug, the
back section of the sorbent, and the retaining urethane foam plug in a
second clean, dry vial. The front and back sections are analyzed
separately.
(2) Desorption of Samples
Prior to analysis, pipet 5.0 ml of hexane into each vial.
Florisil particles should not be allowed to cling to the glass above the
solvent. A minimum . desorption time of 10 minutes Is required before
analysis.
(3) Gas-liquid chromatographic conditions for PCB
determination by this procedure are:
(A) Nitrogen carrier gas flow rate, 60 ml/minute.
(B) Injector temperature, 300 C.
(C) Interface and detector temperatures, both 325 C.
(D) Column temperature, 180 C. '
775503
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GENP 007102
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(4) Sample Injection The solvent-flush technique is recommended for injection of materials into the GLC apparatus. With this method, the following procedure would be used to inject 4 yl of sample. Three microliters of hexane would be drawn into the syringe, followed by 1 til of air, followed by 4 til of sample solution. After the needle is removed from the sample solution, 1 additional ul of air is drawn into the syringe to minimize evaporation at the tip of the needle. The plunger now rests at the 9-yl mark. Inject at least 7 /il of the syringe contents into the gas chromatogram. Not less than 1 til of flush-solvent should be used. Larger volumes of flush may give a solvent peak which interferes with sample component peaks. The syringe must be cleaned with hexane after each injection. (5) Preliminary Analysis Using the solvent-flush method of subsection b(4), inject 1 til of sample and 1 til of flush-solvent at the conditions specified under subsection b (3). If the sample is too concentrated, further dilutions will be necessary to bring the concentration of the sample solution into the linear range of the electron capture detector. Once the concentration of the sample is appropriately adjusted, its chromatogram should be compared to that of a standard to determine if the air sample is qualitatively different in composition from the standard. If there is little difference between the two chromatograms, then proceed with the standard analysis using the PCB mixture for standardization, subsection b(6). On the other hand, should there be a significant difference between the two chromatograms (such that comparison with the PCB mixture could result in
203 775504
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gross error), then use the alternate procedure for standardization,
subsection b(7).
(6) Standard Analysis
Select at least five prominent peaks in the sample chromatogram and compare
their heights or areas with those of the standard. Calculate the
concentration of PCBs by comparing the heights or areas of the selected
peaks in the sample chromatogram of those in the standard chromatograms of
known amounts of material.
(7) Alternate Standardization Procedure
A 200-jil aliquot of the sample is placed in a 13-mm x 100-mm culture
tube and the hexane is slowly evaporated with dry nitrogen until 10 yl or
less remain. Do not allow hexane to climb the tube during evaporation and
do not allow the sample to evaporate to dryness. Immediately add 0.2-0.5
ml of distilled antimony pentachloride with a disposable pipet as rapidly
as possible (antimony pentachloride decomposes rapidly in air) and cap the
tube. The sample should remain light yellow after this addition, but if
the 8ample turns dark brown or black, it must be discarded and another
aliquot of that sample must be used. All samples are placed together in a
8and bath. There should be no liner in the cap of the tube, since most
liners are attacked by antimony pentachloride.
A sample of
decachlorobiphenyl is treated in a manner similar to the samples. The sand
bath containing all of the treated samples is placed in a preheated oven at
160 C for at least 3 hours. Samples may also be treated overnight. After
perchlorination, the sand bath is removed from the oven and the samples are
removed from the sand and allowed to cool to room temperature. To each
sample is added dropwise 0.5 ml of 207. hydrochloric acid. This mixture is
204 775505
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then extracted four times with 1-2 ml of hexane each time. Each extract is
passed through a funnel containing approximately 0.5 g of anhydrous sodium
sulfate (retained by a glass wool plug) into a 10-ml volumetric flask. The
volume of the sample is brought to 10 ml by rinsing the pipet, sodium
sulfate, and funnel tip with hexane. The funnel should not rest on thezlip
of the flask during filtration. The glass wool plug and sodium sulfate in
the funnel are replaced after each sample. An aliquot of the sample
solution is injected under the GLC conditions described above. The
solvents flush technique is recommended using 2 fd of solvent back flush
and 6 til of standard or sample solution. The syringe must be cleaned with
hexane after each injection. The height or area of the decachlorobiphenyl
peak is compared to that of the decachlorobiphenyl standard and the weight
of decachloroblphenyl present is calculated.
(8) Gas-liquid
chromatographic
conditions
for
decachlorobiphenyl determination:
(A) Nitrogen carrier gas flow rate, 90 ml/minute.
(B) Injector temperature, 300 C.
(C) Interface and detector temperature, 325 C.
(D) Column temperature, 220 C.
(c) Determination of Desorption Efficiency
NIOSH has found average desorption efficiency is >99.3%, thus,
results of sample analyses need not be corrected for desorption efficiency.
Calculations (a) Standard Analytical Procedure The following are the steps in the calculation of concentrations of 205 775506
GENP 007105
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FCBa in air vhen determined with a PCB mixture aa the atandard.
(1) Add the heights or areaa of several selected prominent
peaks (at least five) in the chromatogram, compare with the total heights
or areas of those same peaks in the standard, and read the concentration of
the sample solution (ng/ml) from the standard curve.
(2) Multiply the concentration, in ng/ml, of the sample
solution by the total volume, in ml, of the sample solution and calculate
the weight of PCBs in the sample. Make corrections for the blanks if
necessary.
.
(3) Add the weights found on thefront and the back
sections of the tube to find the total weight of PCBs in the air sample.
(4) Divide the total weight of the PCBs in the air sample -
by the volume, in liters, of air sampled and report the PCB concentration
in ng/llter or its equivalent in pg/cu m.
(b) Alternate Standardization Procedure
The following are the steps in the calculation of concentrations of
PCBs in air using the perchlorlnatlon method.
(1) The height or area of thedecachloroblpheny1 peak in
the chromatogram of the sample aliquot is compared to the height or area of
the decachloroblpheny1 peak in the chromatograms of the standard. The
concentration of decachloroblphenyl in the sample aliquot is read from the
standard curve.
(2) The concentration of decachloroblphenyl in this aliquot
(ng/ml) is multiplied by the total volume (ml) of the sample solution to
give the total weight of PCBs in the sample as decachloroblphenyl.
=5
775507
206
WATER PCB-SD0000056867
(3) The weights of FCBs, as decachlorobiphenyl, found on the front and back sections of the tube are summed, corrections for blanks are made, and the total weight of PCB, as decachlorobiphenyl, in the air sample is calculated.
(4) The total weight of PCB is divided by the volume of air sampled and the air concentration is reported in ng/liter or its equivalent In fig/cu m.
207 775508
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XI. APPENDIX III MATERIAL SAFETY DATA SHEET
l4 lfcJi *!
'
rS-'M f l! I f : rBI M'
,<MSUrl!ki**,i7 ; *
General instructions for preparing a Material Safety Data Sheet
(MSDS) are presented in this chapter. The examples used in the text are
for illustrative purposes and are not intended to apply to any specific
compound or product. Applicable information about a specific product or
material shall be supplied in the appropriate block of the MSDS.
The product designation is inserted in the block in the upper left
comer of the first page to facilitate filing and retrieval. Print in
upper case letters as large as possible. It should be printed to read
upright with the sheet turned sideways. The product designation is that
name or code designation which appears on the label, or by which the
product is sold or known by employees. The relative numerical hazard
ratings and key statements are those determined by the guidelines in
Chapter V, Part B, of the NIOSH publication. An Identification System for
Occupationally Hazardous Materials. The company identification may be
printed in the upper right corner if desired.
(a) Section I. Product Identification
The manufacturer's name, address, and regular and emergency telephone
numbers (including area code) are Inserted in the appropriate blocks of
Section I. The company listed should be a source of detailed backup
information on.the hazards of the material(s) covered by the MSDS. The
listing of suppliers or wholesale distributors is discouraged. The trade
name should be the product designation or common name associated with the
material.
_
'
The synonyms are those commonly used for the product, especially
i
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GENP 007108
WATER PCB-SD0000056869
formal chemical nomenclature. Every known chemical designation or competitor's trade name need not be listed.
(b) Section II. Hazardous Ingredients The "materials" listed in Section II shall be those substances which are part of the hazardous product covered by the MSDS and individually meet any of the criteria defining a hazardous material. Thus, one component of a multicomponent product might be listed because of its toxicity, another component because of its flammability, while a third component could be Included both for its toxicity and its reactivity. Note that a MSDS for a single component product must have the name of the material repeated in this section to avoid giving the impression that there are no hazardous ingredients. Chemical substances should be listed according to their complete name derived from a recognized system of nomenclature. Where possible, avoid using common names and general class names such as "aromatic amine," "safety solvent," or "aliphatic hydrocarbon" when the specific name is known. The "%" may be the approximate percentage by weight or volume (indicate basis) which each hazardous ingredient of the -mixture bears to the whole mixture. This may be indicated as a range or maximum amount, ie, "10-40% vol" or "10% max wt" to avoid disclosure of trade secrets. Toxic hazard data shall be stated in terms of concentration, mode of exposure or test, and animal used, eg, "100 ppm LC50-rat," "25 mg/kg LD50akin-rabbit," "75 ppm LC man," or "permissible exposure from 29 CPU 1910.1000," or, if not available, from other sources of publications such as the American Conference of Governmental Industrial Hygienists or the
209 775510
GENP 007109
WATER PCB-SD0000056870
.1*,1 lii*'
American National Standards Institute Inc. Flashpoint, shock sensitivity
or similar descriptive data may be used to indicate flammability,
reactivity, or similar hazardous properties of the material.
(c) Section III. Physical Data
The data in Section III should be for the total mixture and should
Include the boiling point and melting point in degrees Fahrenheit (Celsius
in parentheses); vapor pressure, in conventional millimeters of mercury (mm
Hg); vapor density of gas or vapor (air 1); solubility in water, in
parts/hundred parts of water by weight; specific gravity (water - 1);
percent volatiles (indicate if by weight or volume) at 70 degrees
Fahrenheit (21.1 degrees Celsius); evaporation rate for liquids or
sublimable solids, relative to butyl acetate; and appearance and odor.
These data are useful for the control of toxic substances. Boiling point,
vapor density, percent volatiles, vapor pressure, and evaporation are useful for designing proper ventilation equipment. This Information is
t
also useful for design and deployment of adequate fire and spill
containment equipment. The appearance and odor may facilitate
identification of substances stored in improperly marked containers, or
when spilled.
(d) Section IV. Fire and Explosion Data
'
Section IV should contain complete fire and explosion data for the
product, including flashpoint and autoignition temperature in degrees
Fahrenheit (Celsius in parentheses); flammable limits, in percent by volume
in air; suitable extinguishing media or materials; special firefighting
procedures; and unusual fire and explosion hazard information. If the
product presents no fire hazard, insert "NO FIRE HAZARD" on the line
210 775511
GENP 007110
WATER PCB-SD0000056871
labeled "Extinguishing Media." (e) Section V. Health Hazard Information The "Health Hazard Data" should be a combined estimate of the hazard
of the total product. This can be expressed as a TWA concentration, as a permissible exposure, or by some other indication of an acceptable limit. Other data are acceptable, such as lowest LDSO, if multiple components are involved.
Under "Routes of Exposure," comments in each category should reflect the potential hazard from absorption by the route in question. Comments should indicate the severity of the effect and the basis for the statement, if possible. The basis might be animal studies, analogy with similar products, or human experiences. Comments such as "yes" or "possible" are not helpful. Typical comments might be:
Skin Contact--single short contact, no adverse effects likely; prolonged or repeated contact, irritation, and cracking. Readily absorbed through the skin with severe systemic effects.
Eye Contact--some pain and mild transient irritation; no corneal
scarring.
.
"Emergency and First Aid Procedures" should be written in lay language and should primarily represent first-aid treatment that could be provided by paramedical personnel or individuals trained in first aid.
Information in the "Notes to Physician" section should include an-; special medical information which would be of assistance to an attending physician including required or recommended preplacement and periodic medical examinations, diagnostic procedures, and medical management of overexposed workers.
775512 211
WATER PCB-SD0000056872
(f) Section VI. Reactivity Data
The comments in Section VI relate to safe storage and handling of
hazardous, unstable substances. It is particularly Important to highlight
instability or incompatibility to common substances or circumstances such
as water, direct sunlight, steel or copper piping, acids, alkalies , etc.
"Hazardous Decomposition Products" shall Include those products released
under fire conditions. It must also Include dangerous products produced by
aging, such as peroxides in the case of some ethers. Where applicable,
shelf life should also be indicated.
(g) Section VII, Spill or Leak Procedures
Detailed procedures for cleanup and disposal should be listed with
emphasis on precautions to be taken to protect workers assigned to cleanup
detail. Specific neutralizing chemicals or procedures should be described
in detail. Disposal methods should be explicit Including proper labeling
of containers holding residues and ultimate disposal methods such as
"sanitary landfill," or "incineration." Warnings such as "comply with
local, state, and federal antipollution ordinances" are proper but not
sufficient. Specific procedures should be identified.
(h) Section VIII. Special Protection Information
Section VIII requires specific information. Statements such as
"Yes," "No," or "If Necessary" are not Informative. Ventilation
requirements should be specific as to type and preferred methods. Specify
respirators as to type and NIOSH or US Bureau of Mines approval class, ie,
"Supplied air," "Organic vapor canister," "Suitable for dusts not more
toxic than lead," etc. Protective equipment must be specified as to type
and materials of construction.
212
775513
WATER PCB-SD0000056873
(i) Section IX. Special Precautions "Precautionary Statements" shall consist of the label statements selected for use on the container or placard. Additional information on any aspect of safety or health not covered in other sections should be inserted in Section IX. The lower block can contain references to published guides or in-house procedures for handling and storage. - Department of Transportation markings and classifications and other freight, handling, or storage requirements and environmental controls can be noted. (j) Signature and Filing Finally, the name and address of the responsible person who completed the HSDS and the date of completion are entered. This will facilitate correction of errors and identify a source of additional information. The MSDS shall be filed in a location readily accessible to workers potentially exposed to the hazardous material. The MSDS can be used as a training aid and basis for discussion during safety meetings and training of new employees. It should assist management by directing attention to the need for specific control engineering, work practices, and protective measures to ensure safe handling and use of the material. It will aid the safety and health staff in planning a safe and healthful work environment and in suggesting appropriate emergency procedures and sources of help in the event of harmful exposure of employees.
775514 213
GENP 007 ] 13
WATER PCB-SD0000056874
MATERIAL SAFETY DATA SHEET
MANUFACTURER'S NAME AOORESS
TRADE NAME
1 PRODUCT IDENTIFICATION
REGULAR TELEPHONE NO. EMERGENCY TELEPHONE NO.
SYNONYMS
II HAZARDOUS INGREDIENTS
MATERIAL. OR COMPONENT
% HAZARO DATA
BOILING POINT, 760 MM MG SPECIFIC GRAVITY (MjO-ll VAPOR OENSITY IAIR`11 % VOLATILES by VOL APPEARANCE and GOGH
III PHYSICAL DATA
MELTING point
vapor pressure
SOLUBILITY in MjO, % BY VT EVAPORATION RATE IBUTYt ACETATE-II
214 GENP007114
775515
WATER PCB-SD0000056875
flash point
(TEST METHOD!
IV FIRE AND EXPLOSION DATA
AUTOIGNITION TEMPERATURE
flammable limits in air. % by vol.
EXTINGUISHING MEDIA
LOWER
UPPER
SPECIAL FIRE FIGHTING PROCEDURES
UNUSUAL FIRE AND EXPLOSION HAZARD
HEALTH HAZARD DATA
V HEALTH HAZARD INFORMATION
ROUTES OF EXPOSURE INHALATION
SKIN CONTACT SKIN ABSORPTION
EYE CONTACT INGESTION EFFECTS OF OVEREXPOSURE ACUTE OVEREXPOSURE CHRONIC OVEREXPOSURE
EMERGENCY ANO FIRST AIO PROCEDURES EYES SKIN. INHALATION.
INGESTION
NOTES TO PHYSICIAN
5.53.6 215
00TU5
WATER PCB-SD0000056876
VI REACTIVITY DATA
CONDITIONS CONTRIBUTING TO INSTABILITY INCOMPATIBILITY HAZARDOUS DECOMPOSITION PROOUCTS
CONDITIONS CONTRIBUTING TO HAZARDOUS POLYMERIZATION
VII SPILL OR LEAK PROCEDURES
STEPS TO BE TAKEN IP MATERIAL IS RELEASED OR SPILLED
NEUTRALIZING CHEMICALS WASTE DISPOSAL METHOD
VIII SPECIAL PROTECTION INFORMATION
VENTILATION REQUIREMENTS
SPECIFIC PERSONAL PROTECTIVE EQUIPMENT RESPIRATORY (SPECIFY IN OETAIU EYE GLOVES
OTHER CLOTHING AND EQUIPMENT
yjssi'1
GB^NP 007116
WATER PCB-SD0000056877
TRECAUTIONARV statements
IX SPECIAL PRECAUTIONS
other hanoong and
STORAGE REQUIREMENTS
ERU>AREO 8V AOORESS GATE
775518 217
G17NP 007117
WATER PCB-SD0000056878
TABLE XII-1
i'
CHEMICAL AND PHYSICAL PROPERTIES OF SOME AROCLORS
Aroclor
Chlorine, % w/w
Distillation Range, C
(corrected)
Density g/ml 25 C
Flash point*
F
FirePoint*
F
Appearance
1221 1232 1242 1248 1254 1260 1262 1268
20.5-21.5 31.4-32.5
42 48 54 60 62 68
275-320 290-325 325-366 340-375 365-390 385-420 390-425 435-450
1.18 1.26 1.38 1.44 1.54 1.62 1.64 1.82
286-302 349
Clear, mobile oil
305-310 460
99
384-356 none**
99
379-384
19
99
none**
19
Light-yellow visous liquid
99 Light-yellow soft, sticky resin
91 99 Light-yellow sticky, viscous resin
M - 99
Uhlte to off-white powder
Cleveland Open Cup None to boiling point
ui Adapted from reference 1 M
(D
GENP 007118
WATER PCB-SD0000056879
219
GENP 0 0 7 1 1 9
TA1II.K XII-2 tjr \1 H AliVK AMI PKItl'KNT CIIMUtOIIII'IIKN Yl. ANI IIIPIIKNYI. COMPOSITIONS OF COMMKItCi Al. PCII PltKPAIt ATIONS
(({uhIiIhIivi'Iv mapir peaks M. minor penkn - m, amliiKunua identities - ?; <|uaiilitntively. percentages rounded)
Cl.-Substituted Positions
Commercial Preparation Designations tirade names omitted)
1221 1221 1221 1221 12)2 1016 1242 1242 1242 1241 1241 1254 1254 1254 ISO 12S0 1260
0 13 16 m 16 m 05 m
mm
m
2 28 32 m 35 m 1 m 08 m m
mm
3 3m3
4 19 19 m 20 m
2
mm
23 24 4
3
04 2 1 <0 7 m <0 I
mm
25 02
It
mm
2 6 03
04
li
m
2.2 9 5 m 5 m 7 m <10 14 m
2.3'
3
m
2
m 1
m
m .M
m
24 14 10 m II m 11 m <5 M . m 05
m m m
m m m
34 1
m
m
3 5 Ir
3.3
3 4' 1 4.4' 6 4 m 4 m 2
m IM
<3 <3
m
m
2 34
2.35
2.36
2.2 .3
m5m
M7 m
2.3.3'
01
li M?
2.3.4 It
2.4 5
2 46 2.2'.4 2.3'.4
03 ID
m
m
4
m
11 M
m
1
m m 4 m <15 M m <13
m
(D
m m
2.4 4' 2 25
02 06
m m 4 m. 7 M> m 3
06 m 12 m
2 M m 01
m
m
2 3.5
02
9 m M m <13
2.4'.5
02
m m 10 m
mm
mm
<1
o
2 2 .6
m1m
mm
mm
U1 2 3 6 03 M?
in to
2.4 6
2M
mm
o
3.4 5 2 34
01
It m
16 M m 21
03 m
m
3 3' 4
m
3 4 4'
2M
m
WATER PCB-SD0000056880
TABLE Xll-Z (Continued) QUALITATIVE AND PERCENT CHLOROBIPHENYL AND BIPHENYL COMPOSITIONS OF COMMERICAl! PCB PREPARATIONS
(Qualitatively major peaka = M, minor peaka *> m,amblguoua identltlea = ?; quantitatively, percentage rounded)
CL-Subatltuted Poaitiona
Commercial Preparation Dealgnationa (trade namea omitted)
1221 1221 1221 1221 1232 1016 1242 1242 1242 1241 1241 1254 1254 1254 151 1260 1260 1260 160
2.3.5
ii
3.3.5 3.4.5
ir
2.3.45
2.3.4.6
2.3.56 2.2'.3.4 2.3.3 .4 2.3.44'
2.2.3 5 2.3.3'.5 2 3.4 5
31 04 M 1 m
m m in M?
02
07
2.2.36
2.3.3'.6
NKO>>
2.34.6 2.2.4.S
2.324.5
2.4.425
2.224.6
2.324.6
2.4.426
223.4.5
<2
6 MI
m
Ir M?
<2 Ill m Ii
Mf
21 m HI
3.324.5 3.4.425 2.223.3' 2.2.34 2.2.35' 2.2236' 2.3.324
1 Ii In 1
m 4n
m m 4 H 2 <04
1
2.3.325'
2.224.4'
m 1m
m
2.224.5'
-J <1
2.2.46
in 2.324.4'
3m 01 Ir m
12 III m 16 m mm
1
in 2.324.5'
to
H
2.325.5'
M?
2.225.5*
014
2m
Ir Ml m
m1M5
in
DM
GENP 007120
WATER PCB-SD0000056881
a
<3 3 3
IN
3E
3
V
3
S
304 a e 3
04
3
04
3
vE v
E
e
5a
e
ae
E fi
V
E
E2 E
E2
EEEEE EEE E
EE
EEE
E
e
E
EE
Iffl 10
^^^
^
o
^ ^ w. n w W <> w m w tfl i<i ^ tfl n W in tri W in
^ ^ w us
W m' *n W *n ]S8>. W
enNNNNNNWmn(NNNNW(*lNNNPI
oi04 04 04 04 04 04 04 04 04 04 04 04 04 04 404 04 04 04 04 04 04
m 04 04 04 04 04
2.3.4.5.6
2 2.3 4 5
2.3.3'.4.5
221 775522
GENP 007121
WATER PCB-SD0000056882
MK>
-J -J
tn
ui
to ip
to to
TABLE XII-1 (Continued)
'
QUALITATIVE AND PERCENT CHLOROBIPHENYL AND BIPHENYL COMPOSITIONS OP COMMERCIAL PCB PREPARATIONS
(Qualitatively major peak* M. minor peak* > m, ambiguous Identities * T; quantitatively, percentage* rounded)
CL-Substituted Positions
Commercial Preparation Designation* (trade names omitted)
1121 1221 1221 1221 1211 ISIS 1242
2.2\4.5\
2.r,4.8,8'
2,1',4,4',8 2,1'.4.S`,6 2,3.T.4`,5' 2.3\4.4'.S' 2.3\4'.S.S' 2,S\4'.5',8 3.3'.4,4'.5 S.S'.4.5.5' 2.2M.4.S.S 2.3.3'.4.5.6 2.3.4.4.5.5 2.r.l.l',4.S 2.2\3.4.4'.5 2.2\3.4.5.5' 2.2M.4.5.8' 2.3.3'.4.4'.5 2,3.3'.4.5,5' 2.2\3,3'.4.8 2,f,3.4,4',6 2.2".3.4,S'.8 2.2'.M.8.6` 2.33.4.4.8 2.3.3',4.S'.S 2.2'.3,3',5.S 2.2.3.4.5.5 2.2`.3.5.5'.6 2.2.3.5.S.S' 2,3.3'.4'.5.6 2.3.3'.5.5`.6 2.2'.3,3'.4,4' 2.2'.3.3'.4.5' 2.2'.3.4.4'.5' 2.3.3'.4.4'.5' 2.2'.3.3'.4.6' 2.2'.3.4.4'.6'
1242 1242 1241 1241 1254 1254 12M M 12M 12M 1280 M
m 0.1 <S s
2
1
2 m1 <1
12 M 5
U2
M
M
3
2 2
II 3
mm si m
WATER PCB-SD0000056883
E EE
3 EE 3 3 EE 3
3 VV SeSs 3 aE
in
3E
3E
E
3
SCM
ee
6 EE
E EE SE SE
EE
E EE wE
E
EE
EE
ifl in " w. i/j m .
in' A tn m' *"*.
in n in (n
m' *n *,,' ^ tni ^VO 0 IA
to 0 Mil y us n a mt
i0 n in
nnW
us w us us us
cm cm <--> cm
N fM PW N
(s
\
nn
N
CNd
N
<N
WN
n (M
N
Pg
fM
fV n
m
IN N N N N
N N N N IN (V* rvNNfWfNINNfNNCN
*"* in IA fl US
US US us US us
iN w ru m .
N IN N N N IN N IN N IN 1 IN IN N CM **
775524 223
GENP 007123
WATER PCB-SD0000056884
TABI.E XII-2 (Continued) QUAI.ITATIVK AN!) PERCENT CHLOHORIPIIRNYL AND BIPHENYL COMPOSITIONS OF COMMERCIAL PCB PREPARATIONS
(({unlilalively major peaka = M. minor peaka = m, amhigunua identitlea = ?; quantitatively, percentagea rounded)
('L-Kuhatiluled l`n>ilinns
Commercial I'reparalion Dcaignatinns (trade numea omitted)
1221 J22I 1221 122) 1232 1016 1242
2.3.3'.4.4'.5.5'.6 2.2'.3.3'.4.4'.5.5` 2.2.3.3'.4.4'.5.6' 2.2'.3.3'.4.5.5'.6' 2.2'.3.3'.4.4'.6.6' 2.2'.3.3.4.5.66' 2.2'.3.3'.5.5'.6.6' 2.2'.3.3'.4.4'.5.6.6' 2 2 .3.3 4.5.5'.6.6' 2.2`.3.3'.4.4`.5.5'.6 2.2'.3.3'.4.4'.5.5`.6.6'
m m
Rtleienct No
17 *
16 a
16 a
16
1242 1242 1241 1241 1254 1254 1254 850 1260 1260 1260 860
04 2
m
m
01 5 m
li at
ti m
li li
04 m
m
at m
m
07 07
li
a 14 16 a 16 a 14 7 a 91 8 7
m Oft 16 8
a PW Albro. witlen communication. Noveaibei 1976
NKl
GENP 007124
O o
<J1
I U1 to
I U1
o t
WATER PCB-SD0000056885
beet W. B. Papag orga O. J. Levirwku
Movmbmx 7, 1975
Dr. Miehaal Nodaa
Man*pttjtJiftfttut:
mSrii Xlactrlc Ona fanatic Avanua fittafiald, Km. 01201
Dear Kitei
Z ancloaa tha data concerning polychlorlnatad blphanyl Which you diacuaaad with Dr. Richard. Ihe ancloaad data conlata of tha following
1) Toxicity information on Aroclor 1010.
S) fli Degradation f folyehlorinatod Biphonyla By Micro-organlama- R. A. Baxter, f. t. Gilbert, R. A. Lldgett, J. Kiiepriu and X. A. Vodden.
3) Zdantiflcation of chlorinated dibenaofurane in Anar lean polychlorlnatad biphenylsR W. Rieebrough
4) PolychlorInated Biphenyls - storage, Distribution, Bxcretion, and Rocovaryi Liver Morphology After Prolonged Dietary Ingestion - Virlyn W. Burse, Ranata D. Kiahrough, Bilan C. VilUoaava, Ralph x. Jennings, Ralph X. Under, O. Wayno sovoeool.
I) '
'
4)
Laboratory Modal Ecosystem Studies of tha Degradation and
fata of Redtolabelad Tri, Tatra, and Paniactilorobipbattyl
Ooespnrad with SOB - Robert L. Metcalf, Jamaa R. Batiborn,
to-Xtang Zm and Donald *y*.
'
''
A Comparative Study Of Two folychlorinatad Blphanyl Mixtures CArocion IMt and 1014) Containing 4W Chlorlas on Induction of Hepatic Porphyria and Drug Metabolising SnxyMs.
NEV 028031
741285 WATER PCB-SD0000056886
Dr. Michael Modan
2" -
November 7, 1975
7) Biodegradation of Polychlorinated Biphenyls - E. Scott Tucker, Victor W. Saeger and Orville Hicks.
8) Tissue Residues From Subacute Oral Feeding of Poly chlorinated Biphenyl Dielectric Fluids - Robert G. Kaley, Orville Hicks, William M. Mees, E. Scott Tucker, James p. Mieure, Frederick R. Johannsen and George J. Levinskas.
9) Migration of Polychlorinated Biphenyls in Soil Induced by Percolating Water - E. S. Tucker, W. J. Litschgl, and W. M. Mees.
10) Acute Toxicity Studies with MGS (Aroclor) 1016.
11) Presentation To The Interdepartmental Task Force on PCBs, Washington, D. C. - Monsanto Company.
Yours sincerely.
/deb Enclosures
David Wood Market Manager Dielectrics
NEV 028032
741286 WATER PCB-SD0000056887
Monsanto
'
"o" * ,or*""' David Wood-5t. Louis-B2SD
fti/Bjrci
' *
NfftM'NCt
t
TO :
August 29, 1975
TELEPHONE CALL REPORT 8/29/75
W. B. Papageorge B2SK
5-f Qc-^i^o -cjO
CC:
H. S. Bergen-B2SL C. Paton/T. L. Gossage-B2SC/B2S G. Roush~A2SA G. Levinskas-A2SC SU J. P. Mieure-T2B W. R. Richard/R. H. Munch-T3A/T W. W. Withers-B2SA
CALL FROM:
Dr. J. R. Allen University of Wisconsin
(608)263-3524
Dr. Allen called about Dibenzylfurans and Dioxins in Chlorinated Biphenyls as a result of his reading the Risebrough paper. He is concerned about levels of these compounds in the Aroclors which he is using for his U. of Wisconsin feeding studies since he is unclear as to potential interferences in results which can be ascribed to PCB per se or contaminants in PCB.
He asked if we could check samples to be used in his studies
to determine positively if contaminants were or were not present in those specific samples. I said that I did not believe our analytical techniques were fully developed to the stage where we were confident that we could properly
consider ourselves able to meet his need., I told Dr.
Allen that we would discuss his' request and call him next
week.
.
. /deb .
, '
David Wood
U <
NEV 018503
726554 WATER PCB-SD0000056888
Mon$a(U(
n
|i I * Ml l* |
10
V.
...................
B.V.N. Hardy, London
l?th January, 1967
Aroclor - Sweden
imra/AHW '
P.G Benignus, St LoudLe G.R. Buchanan, St* Louis B.S, Cameron, Brussels Br. R Barnet Kelly, St. Louis GR* Graham, New York R.A. Steenrod, St. Louis . B. Wood, Brussels J.A* LVans, London R.A. Baxter, Ruahon
'JAN : 6 1961
On 2nd January 1967 Mr. A. Richardson of Shell Chemicals' Tunstall laboratory, Sittingboume, Kent talked with me over the telephone concerning the Swedish Press report relating to the identification of "Polyciilorinated Biphenols" as trace contaminant in sea birds, fish etc. Richardson has been working for scone years on the similar problem with insecticides such as DOT, which are known to have wide distribution in trace quantities. He had already found that the chlorine-oontaining residue contained substances more stable than DDT. and just as SBren Jensen reports h has obtained spectrographic evidence that these are very similar if not identical with Aroclors. He has obtained samples of Aroolors 1242, 1254* 1262 and 5460 from us,' and would now like to have small samples of any chemically pure Aroclor constituents which we may be able to supply. Milligram quantities would suffice for his purpose.
Mr. Richardson was quite sure that the compounds reported to be "polychlorinated biphenols" are really meant to be polychlorinated biphenyls and as support he has sent me a copy of the synopsis of a paper entitled "Pesticide Analysis t Presence of Polychlorinated Biphenyls at Residue Analysis of Biological Samples" by SBren Jensen and Gunner Widmark (photocopy attached). . ^
I discussed with Richardson the soundness of Jenserfs claims, and waa assured that Ills work and findings are sound. Jensen is on
the staff of the.Institute of Analytical Chemistry, University of Stockholm. A note on the staff and work of the Institute is attached.
Prom this you will see that Jensen is wholly concerned with the analysis of chlorinated pesticides and with the work of stations for
routine analysis.
'
I would be glad if Br. Baxter and Br. Buchanan would arrange to Bend me milligram samples of any pure Aroolor constituents that may be available at Ruabon and St. ^ouis respectively.
1
PLAINTIFFS
Ij 1
/VEXH7IBiITT
NfcV 022115 732170
WATER PCB-SD0000056889
Monsanto
. 'm: a | (
R.A. Dnxtcr
19lh August 197 5
I,LN
II I I Ml NCI
TO
CHLORINATED D1BENZOEURANS
rad/ak
.
R.E. Keller - St Louis
. Richard S, ^Bergen
Papagcorgc Wood A. Lidgett J.N. Haggart
St Louis St Louis St Louis St Louis LLN BXLS
Bob,
Reference your memo of August 15tH, Alf VoSficn has had some contact with the Bayer technical people and they nq.ve^^yfomised to come back to us after the vacation period. We will follow this up again but I don't expect anything more positive until early September. To speed tilings up we are attempting tc arrange an exchange of samples through the commercial channels and will send these on to you as soon as we get them. .
From the preliminary discussions it 6eemed that Bayer had not done any serious in-house work on the analysis of dibenzofurans in PCBs.
Predelec were even less forthcoming and didn't want to commit.
Now that Risebrough's paper has appeared in Nature we may see more inter by the European PCB producers. We will keep you in the picture.
Regards,
R.A. Baxter
PLAINTIFF'S I jEWXHIBIT II
729462 WATER PCB-SD0000056890
November 1975
ife
l
1i , -
t \
{ >r whether
-nuch or
Session V:
ECONOMICS AND SUBSTITUTES
Warren Muir, Ph.D.* Session Chairman
I
* Senior Staff Member for Environmental Health, Council on Environmental Quality, Washington, D.C.
NEV Q26149
WATER PCB-SD0000056891
I
INTRODUCTORY REMARKS
Warren Muir, Ph.D.
I guess we have all had an opportunity to hear about health and ecological Impact and other aspects of PCB's In the last day and a half. The history of PCB's, as I am sure most of you are aware, is several years old. By 1971 and 1972 there was sufficient concern over their potential environmental effects that a Federal task force was created under the sponsorship of the Council on Environmental Quality and the Federal Council for Sci ence end Technology, which looked into the situation
and made a variety of recommendations. In addition, at that time the Monsanto Chemical
Company developed a restricted sales policy with regard to uses of PCB's, and also shortly thereafter, the Organi zation for Economic Cooperation and Development had an International agreement with regard to uses of PCB.
All of these actions were directed in one fashion or another toward inappropriate uses of the chemical. Yet, as of this date, there is no Federal authority to control the use of these chemicals, despite 5 years of consider ation of toxic substances control legislation.
This particular session of the conference deals with economics and substitutes; we will have a presentation or a brief description of two economic case studies that have been done on PCB's, and then several speakers will discuss the substitutability or nonsubstitutability for uses of PCB's.
In dealing with environmental problems such as PCB's and a variety of other chemicals, I am sure you are aware that there is a great deal of scientific uncertainty with regard to particular health or ecological impacts. For example, there is a certain amount of uncertainty as
to whether or not something is carcinogenic or whether
it can bioaccumulate.
There typically appears to.be, however, a much
greater uncertainty about the economic implications or
the economic impacts of any action that might be taken
to mitigate the suspected problems. >Much of this arises
from uncertainty, about substitutes and also about the
inability to predict the actual individual or corporate responses that would be made under a given type of
regulatory action or other type of mitigating action.
Thus in my view, there is much greater economic uncer
tainty in many of these issues than there is scientific
uncertainty.
:
Also, irrespective of all the uncertainties, we know
that the further along in the chemical marketing and
development process, the longer it has been manufac
tured, and the larger the market, generally the greater
the health and environmental effects of the particular
chemicals and the greater the economic impact there is
of mitigating action, to the extent that they are neces sary.
Thus, if we are to deal with problems such as PCB's,
we must change our approach toward environmental
chemical problems; we must get out of a reactive pos
ture. We must undertake the task of identifying poten
tial hazardous chemicals early in the development
process. By so doing, health and ecological problems can
be avoided before they develop. And, by so doing, the
economic dislocation and impacts from any potential
regulatory action will be eliminated or minimized to the
benefit of all.
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PCB's IN CAPACITOR APPLICATIONS Richard L. Rollins*
Abstract
Alternating current (AC) capacitors have used a grade of polychlorinated biphenyls (PCB's) since the 1930's. Long life, high reliability and a high degree of flame retardancy are imparted to the capacitors by these fluids.
The latter characteristic is very important In applica tions where high exposure to the general population exists such as in fluorescent lights and television sets. The main disadvantage with the fluid is its long persist ence in nature. When the capacitor industry became aware of the environmental problem, it generated guide lines for handling and disposal of the material, then voluntarily imposed these restrictions upon itself. Now of the 70,000 pounds per day processed, only 7 pounds are being discharged into plant water effluents. Liquid waste materials are sent to proper incineration facilities and solid waste materials are placed in sanitary landfills to prevent escape into the environment. For 4 years the industry has been using a significantly more biodegrad able grade of Aroclor identified as 1016 by Monsanto. In that time. Arocfor 1016 has not been identified as a PCS commonly found in the environment. Non-PCB mate rials are continuing to be evaluated, but there are not dielectric fluids available today which can be considered an acceptable substitute for PCB's in the broad range of AC capacitors.
On behalf of the electronic industrial association and the manufacturers of PCB capacitors, I appreciate this opportunity to present our point of view. I will discuss PCB capacitors, the industry's response to the environmental problem, and possible alternative candi dates to PCB's.
Manufacturers of AC capacitors have used PCB's since the early 1930's, and have used them almost ex clusively sinc World War II. They are presently used, for example, in capacitors for fluorescent lighting, air con ditioners, and television sets. These capacitors are in the plant where you work, in the home, and in public gathering facilities. They are therefore near you a high percentage of the time. Manufacturers are very cognizant of their responsiblities in providing a capacitor that will operate satisfactorily in these applications for providing long life and high reliability at a reasonable cost.
Vico President for Engineering, Jard Corporation, Bennington, Vermont.
The consequence of these requirements in a com petitive marketplace is that the products and their com ponents are constantly being reevaluated to Increase life, increase reliability, decrease size, and decrease cost. The capacitor manufacturer indeed daily sees pressures for improvements. It is, therefore, an obvious question to ask why are PCB's still used after 40 years during which the best capacitor research and development scientists in the United States were constantly seeking substitutes.
One of the reasons lies in the nonflammability of the PCB material. Because of applications, such as light ing, where personnel end equipment safety are para mount, capacitors must be manufactured since they not only fail infrequently but also fail safely. In applications such as the World Trade Center in New York, where 250,000 fluorescent lights are installed, it is obvious that high reliability and a nonflammable capacitor character istic are mandatory.
A capacitor which fails violently and contains a flammable fluid could create a serious problem, especial ly in densely populated buildings, giving visions of a towering inferno. The Consumer Products Safety Com mission, as an example, has shown considerable concern over television set fires and has requested Underwriters' Laboratories to develop standards for safety for tele vision set receivers.
A second reason lies in the reliability of the product as it is known today. Presently, the capacitors our com panies manufacture have a survival rate per year greater than 99.9988 percent. The requirement that more than 95 percent of our capacitors must survive after 13 years of normal application conditions must also be met.
The test time and the amount of test necessary to guarantee the above reliability is mind boggling to say the least. Many thousands of units and millions of unit hours at or referred to application conditions are required to satisfy our statisticians that any change in product will conform to these present day standards.
Even with the large amount of previous testing and history on the PCB-containing capacitor, there have been many instances which despite all controls in existence cause consumer concern due to extreme failure rates. That is at a rate greater than 10 percent.
The first, occurred in 1957, when a variation in the quality of the PCB fluid, as synthesized, resulted in a highly unstable capacitor. Standard analytical tests in use at the time did not detect the quality difference. The result was a large number of capacitors failing in a very short period of application life.
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The consequence was the requirement by' the customer that the capacitor manufacturer not only pro vide compensation for the cost of the capacitor, but the cost of the equipment which contained the capacitor, plus the labor charge for placing the equipment in the installation. The total replacement cost the manufac turer 100 times the original price of the capacitor.
The second Instance of numerous failures occurred 6 years later, this time involving the capacitors of most manufacturers. In this circumstance reduced-size capaci tors were tested and approved by industry-accepted accelerated life testing and a new.size was shipped to
customers. Approximately 1 year later, up to 16 percent of
these capacitors began failing in some applications. A subsequent modification in the accelerated-tife testing based upon findings in the field failure analyses now provides proper screening to eliminate the chance of such a problem occurring. Therefore the AC capacitor industry now does very extensive evaluations before re leasing new designs or using new materials.
The capacitor industry became aware that PCB's were possible environmental problems in 1B70. Soon thereafter, In 1971, a committee was formed under the sponsorship of the American National Standards Insti tute, ANSI, to develop standard industry guidelines for the handling and disposal of capacitor grade PCB's. An interim standard .was published as an official standard proposal by the National Electric Manufacturers Associa tion, NEMA, in January 1973. And a final document, C107.1 1974, was published in January 1974.
Briefly, properly planned housekeeping, considera tions for employee safety, and scrap disposal procedures were detailed. Today, to the best of my knowledge, all manufacturers of PCB capacitors in the United States have applied these guidelines for the handling and dis posal of PCB's.
The success of the manufacturer's control in han dling practices is apparent from the fact that of the approximately 70,000 pounds per day used, less than .01 percent or 7 pounds per day is discharged into the water effluents of the plants. The ANSI guidelines also recommended that the capacitor companies change from Aroclor 1242 to a PCB with less toxic effects which Monsanto identified as Aroclor 1016.
Here it must be pointed out that various grades of PCB's cannot, as so often is assumed, be classified as having the same chemical, physical, or biological charac teristics. For Instance, In "A Comparative Study of Two Chlorinated Biphenyl Mixtures ..by Goldstein et al,, significant differences were shown to exist in the biologi cal effects of Aroclor 1242 and 1016 on equal doses of the two mixtures. Aroclor 1016 also reduces by greater
than 04 percent those higher homologs existing in
Aroclor 1242 which were the most persistent in nature.
With these benefits, and without sacrificing the capacitor
characteristics, atl capacitor manufacturers began using
the new material by 1972, despite the fact that it was B0
percent more expensive.
_
After 4 years of use by the capacitor industries,
Aroclor 1016 has not been identified as a PCB that is
commonly found in the environment. Nor should it be
suspected that 1016 would be commonly found, because
the industry is exercising control over waste disposal
from Its capacitors, so that there is little or no oppor-
tunlty for leaking PCB's.
Our industry believes it is much more important to
reduce the environmental problems and to allow con
tinued use of the capacitor-grade PCB than to be con
cerned with the material cost Increase and immediately
turn to a substitute which is not thoroughly evaluated
and may be flammable.
Alternates have been considered ever since the origi
nal introduction of PCB's. The substitutes must be not
only a satisfactory dielectric fluid providing acceptable
life, reliability, and safety, but in addition must not
cause environmental problems. Our experience with
PCB's has demonstrated that some material will escape
into the environment through processing and handling. Therefore, alternate fluids must be evaluated on this
basis. The effects on man and his environment must be
determined before the product is introduced. It would
be a very serious error to replace capacitor-grade PCB's
with a fluid which eventually becomes a greater threat to
man. '
Further PCB modification which would provide
even less toxicity and persistence in nature but still
maintain good dielectric properties and good non
flammability would seem to be one alternative to
Aroclor 1016. Our companies respectfully urge
Monsanto to pursue this possibility.
Non-PCB alternatives are now being offered and suggested. Some are new and some have been available
for many years. The industry's position on these is as
follows.
Mineral oil is a flammable fjuid which was replaced
by PCB's in the 1930's, Capacitors using it arc B0 to 100
percent larger, much less reliable, and much less safe
than those using PCB's. The substitution of mineral oil
necessitates redesign of equipment to utilize the larger
capacitor, an increase in the capacitor manufacture facil
ity, and will result in increased use of basic materials
which ate presently in short supply.
Modified synthetic hydrocarbon oils have been
developed which while flammable would allow capaci
tors to approximate today's size. Samples have been dis-
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trlbuted for testing, but the material is not commercially available.
PhthBlate ester, also a flammable fluid and also with blodegradablllty problems, has been used In certain restricted applications where conditions of limited tem peratures exist. The unknown factors of reliability and safety In the broad consumer use areas such as lighting now prevent its use. Evaluations, however, are continu ing.
Substituted aromatic compounds are possible candi dates, and one has been proposed that has less fire resist ance than PCB's; it is suggested to be a good dielectric fluid but only for high-voltage power factor correction. This, to our estimation, represents only 17 percent of the PCB used In closed systems, and leaves completely unanswered an alternative or alternatives for the remain ing 83 percent of the applications. Some material has been produced but the fluid has not been made commer cially available. In fact, our companies are having trouble obtaining samples from the manufacturer. When samples become available, the time-consuming testing can begin. It has been estimated that 3 years are required before final commercial use after initial testing of a change in capacitor fluids.
Also proposed for limited applications is the use of a plastic film replacing the kraft paper dielectric in the AC capacitor. Although evaluations with the highest quality film have been underway for more than 2 years using the current processing techniques, the reliability of
the product is only 1/20th of that of present capacitors in most applications. Significant additional testing is required to determine if the cause of poor reliability is totally Inherent or If improvements can be made by modifications in capacitor design.
In summary, there are no commercially available fluids which today can be considered a totally accept able substitute for PCB's in the broad range of AC capacitors, nor are there substitute dielectric systems which would satisfy the requirements of reliability and safety in most applications.
, I would like to reiterate that our companies have shown responsiveness to the environmental problems of PCB's by the following actions. 1. Working as a group with government and consumers
In providing guidelines for proper handling and dis posal of capacitor- and transformer-grade PCB's. 2. Reducing discharge levels of PCB's in a 16 capacitor plant. Further reductions are now being planned. 3. Converting to a more expensive grade of PCB's which is less persistent and has less toxic effects. Finally significant differences do exist between Aroclor 1016, which capacitor manufacturers are now using, and material which is predominantly being found in the environment. Our industry believes that all concerned should be aware of the differences. We respectfully urge this awareness in environmental studies and in drafting of regulations.
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THE ECONOMIC IMPACT OF A BAN ON POLYCHLORINATED BIPHENYLS
Duncan MacArthur* and Stephen F. Nagyt
Abstract
The study described below assessed the effects of a hypothetical total ban on PCB's. In order to compile a realistic scenario, the proposed Toxic Substances Con trol Act ms used as a model. A complete phaseout was estimated to take 76 months, and would Involve publica tion of rules, testing, hearings, hatting of imports and manufacturing of PCB's, and depletion of stocks of PCB-containlng products.
Mineral oil was assumed to be the primary substi tute for PCB's, since a major technological breakthrough In the development of alternate fluids is unlikely In the near future.
Minimum estimates are given for the one-time and annual capital expenditures by industry of a ban on PCB's, and for the primary and secondary Impact costs. Intangible Issues, such as the effect of a PCS ban on public safety, are also discussed.
In the course of our work with private and public clients, we have examined polychlorinated biphenyls, PCB's, in a number of areas, ranging from product design to economic impact. The work to be discussed here was completed in 1975 as part of a study to examine the effects of the proposed Toxic Substances Controls Act, as Illustrated by Senate Bill S776 (20 Feb. 75).
We selected as an example a case study to com pletely ban an existing product following the procedures outlined in the proposed bill. We use the case study for following reasons. It provides an example of the com plete analysis required to assess the Impact of a ban; it Illustrates the direct and secondary impact on industry; and It enables us to estimate the economic consequences of a ban on one specific product. In our study, we also highlighted the unquantifiable factors.
In our methodology, and again this was done in the early part of the year, we assume all the steps in the proposed Toxic Substance Control Act as illustrated by Senate Bill S776 are taken. The end result of this is a total ban on PCB manufacture and use. We selected PCB's for illustrative purposes only. Our discussion was not intended to reflect on the actual health or environ mental aspects of the example product.
`Associate Research Director, Foster D. Snell, Inc., Division of Booz, Allen, & Hamilton, Inc., New York, New York.
t Research Director. Foster D. Snell, Inc., Division of Boor, Allen, & Hamilton, Inc., New York, New York.
The scenario for banning the product is estimated to require about'76 months for complete phaseout of prod uct use. Thirty-eight months were estimated for publica tions of the rules, testing, hearings, and so forth. The key element in this period is the 24-month period that we estimated would be required for testing. The key element in months 39 through 76 is phasing out the sale of some manufactured goods, particularly appliances. We also assumed that no legal action would be taken by industry until publication of the final ban on substances occurring after the 38 months of testing and hearings.
A possibility In the scenario of the second 38 months is that industry reguests a judicial review but complies with the review. We estimated the judicial review takes 2 years and results in a complete product ban. In the second 38-month period the following types of activity would go on: documentation for control purposes; monitoring of shipments; limitation of stock piling of PCB products; refining methods to prevent PCB's from entering the environment, such as controlled use and control proposal; stopping the production and import of PCB's dr equipment containing PCB's, and finally banning the manufacture and sale of PCB-containing products.
In the analysis of our PCB's we have tried to consid er the complete life cycle of the product. PCB's are pro duced by one manufacturer in the United States-the trade`'name is Aroclor-and about 40.5 million pounds were produced in 1974. The sale of PCB's is currently restricted to electrical use and casting waxes. In the past they were used as transfer fluids from heat exchangers, hydraulic fluids, and so forth. However, as you know, to avoid potential adverse environmental impact, Monsanto restricted domestic and export sales in 1972 to electric installation equipment applications in which the product is enclosed in a relatively well-maintained container throughout its use. Monsanto and others offer PCB dis posal service.
We found that PCB applications are characterized by their long-term utilization with the majority con trolled by utilities. Transformers, for example, were re ported to last 20 to 30 years, and capacitors to last 7 to 10 years.
The number of transformer manufacturers vary; anywhere from 2 to 10 have produced PCB-containing transformers. Primary use is as nonflammable electric insulating oil. Previous estimates report approximately 5,000 transformers were produced per year with an aver-
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age PCB amount of about 5,000 pounds per transformer.
Value of shipments (1974 data) is estimated at $35 to
$45 million.
'
The number of people using capacitors varies. Esti
mates range from 16 up to 50 capacitor manufacturers.
There are approximately 90 to 100 million units per
year produced with a value about $105 to $147 million.
There are primarily two types: large utility capacitors,
using about 9 to 13 million pounds of PCB's per year,
end small industrial capacitors, using about 17 million
pounds per year.
In the case of casting wax, there is only one manu
facturer In the United States. PCB's represent 30 percent
of the components of the wax. The annual usage is
about half a million pounds. Primarily, it is imported.
We also found another indirect importation of PCB's-in
capacitors in electrical equipment.
The primary transformer users are utilities; others
Include manufacturers of and users of electrically power
ed rail equipment, furnace equipment, and electrostatic
precipitators. About 85 percent of PCB transformers are
used as network transformers by the utilities, and we
estimate that approximately 90 percent of the trans
former uses are controlled by the utilities, either through
ownership or service contracts.
With respect to the capacitor users, electric utilities
use large capacitors and manufacturers and consumers of
goods use small capacitors. Electric utilities use them
primarily for power factor correction, and smaller units
are used for starting and other uses such as fluorescent
lighting. We estimate that about 2 to 3 percent of large
capacitors arc consumed as replacements and about 5 to
10 percent of the small capacitors were consumed as
replacements.
With respect to the casting wax, approximately 98
percent of that is now recycled and the people in the
business maintain that the remaining 2 percent that is
left in the mold is destroyed when the mold is prepared
at high temperatures.
The final step is disposal. Monsanto end others have
specialized incincerator facilities for PCB liquids, primar
ily for large uses such as transformers and capacitors
used by utilities.
The ban of PCB's was estimated to result in a one
time cost of $13.7 million. There would be additional
expenditures of $110 million annually. The ban would
also affect regulatory codes, public safety, and other
intangible areas, and, as always, the net result would be
an increase in consumer costs.
The primary impact, which is on the manufacturer
and users, is estimated at $8.8 billion for one-time costs
and approximately $16 million for annual costs. Key elements in this, surprisingly enough, were "red tape"
required by Senate Bill S776. There are also disposal costs, plant rebuild costs, and salary costs.
Secondary impact on users of PCB's, PCB contain ing products or services, and disposal organizations is estimated at $4.9 billion for one-time costs and $93 bil lion for annual costs. Elements of secondary impacts are primarily new plant rebuilds for increasing the capacitor output of the United States, disposal, and the increased cost of substitutes.
The annual costs reflect the forecasted increased costs of electrical equipment manufacture and use, in cluding replacements of existing equipment. Since the lifetime of targe transformers and capacitors is 20 to 30 years, the additional annual cost, over $110 million, was forecast for the same period.
In the proposed 38-month time period, industry representatives indicated that for primary and secondary transformer use, there would essentially be a shift to mineral oil as a replacement for PCB's, since the environ ment and performance characteristics of other substi tutes are not thoroughly researched. Major technological breakthroughs, such as development of substitute fluids, were not forecast.
We did use minimum cost estimates. The cost of replacing a PCB transformer, for example--not necessari ly the transformer but the vault which is surrounded by the building--has been estimated as varying anywhere from $5,000 to $50,000. We used a figure of about $10,000, which we consider low and very conservative.
The economic impact of changing the regulatory codes cannot be accurately quantified without a detailed survey. However, the impact of the changeover for those localities with regulations was estimated not to cause major dislocation in building activities. We do know that many cities permit only nonflammable, essentially PCB, electrical equipment to be installed in tall buildings; however, others do permit non-PCB transformers with a vault.
Intangible issues include public safety, which would be impacted by a ban on PCB's. Analysis would require a detailed analysis of the tradeoffs between the benefits of the product versus the benefits of the ban. Electrically driven- trains use PCB transformers and it has been re ported that the flammable liquid in the transformer would be a potential hazard. Uses of other transformers in rail cars, if possible, would require redesign and over haul of existing equipment. Use of largo quantities--over 20 gallons of liquid--in buildings would present a poten tial danger even in walls. Insurance underwriters have reportedly studied the problem but nothing has been presented as a request to change rates.
Other intangible areas are in replacements for all types of equipment. Dry transformers, for example, are
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reported to have a low reliability. There are also specific trees, such as replacement capacitors for compact equip ment in which the capacitors cannot be replaced with a non-PCB-containing unit similar In size and characteris
tics, forcing either salvage or scrappage of the equip ment.
In assessing all these costs, we forecasted pass through to the consumer.
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1
THE USE OF DOW CORNING Q2-1090 DIELECTRIC LIQUID IN POWER TRANSFORMERS
Richard H, Montgomery*
Abstract
Dow Coming has developed Q2-1090 Dielectric Liquid to replace askarels in transformers. Five years of laboratory and field testing have shown it to be both efficient and safe. It is now being sold in commercial quantities both for new transformers and for retrofilling old transformers. With some redesign, competitive en tries, and further restrictions on PCB use anticipated, it is expected to have favorable economics. A 3- to 5- year phase-in to completely commercially qualify the liquid in all applications Is planned.
Thank you for the opportunity to come here today to represent the silicone industry, which in the United States consists of the Dow Corning Corporation, the General Electric Corporation, Union Carbide, and Stauffer Chemical. The global silicone industry is now 5 years into a program to qualify dielectric fluid replace ments in both transformers and capacitors. The Japanese silicone industry and Dow Corning Corporation have led this effort to date. As a result of this extremely large effort by the industry, I am very pleased today to make two major announcements.
First, the technology to commercially manufacture a capacitor dielectric fluid with superior dielectric pro perties is being developed. This material appears to with stand any of the high electrical stresses the material would normally be used for in the industry. We plan to make this product commercially available during 1976. At its present state of development, we know of no environmental problems with this particular product. No chemistry would indicate there should be any. But this will be continually studied, as have other products from the silicone industry.
Second, Dow Corning now has commercial produc tion available to manufacture silicone transformer liquids in sufficient capacity to handle the global trans former market, and that is a very large investment. So let me now turn in some detail to the transformer industry and the role silicones can play.
We must remember that today three environ mentally safe transformer systems are available to re place transformers filled with PCB liquids. Gas-cooled,
*New Product Market Manager, Fluids and Lubricants .Marketing, Dow Corning Corporation, Midland, Michigan.
air-cooled dry types, and liquid-silicone-fillcd trans formers will meet almost every need where PCBcontaining transformer fluids are used.
The silicone industry has produced insulating materials for transformers for 26 years. The industry's newest material, a silicone transformer liquid, is now in use in Japan as a direct replacement for PCB-containing transformer oils. In the United States, extensive field testing has been under way for 4 years and at the present time this material is being examined for inclusion in the U.S. National EI.ectrical Code.
Now, to underscore Dow Coming's personal assur ance in the safety, the efficacy, and the efficiency of this liquid, Dow Corning has notified its vendors that we will be specifying silicone-filled transformers for all the new transformers in our production plants around the world. Our existing askarel transformers, in which we have a very heavy investment, are being phased out rapidly through a silicone retrofit program. Over 6 transformers have been installed new or retrofitted in the past year, and this program will accelerate in the spring. It is, of course, not possible in Michigan during the winter months to drain the PCB's satisfactorily and replace these materials with a silicone fluid.
The material that we are talking about Is known today as Q2-1090 dielectric liquid. Basically, Q2-1090 transformer liquid is a dimethyl silicone that has been specially formulated and qualified for use in electrical applications. The technical feasibility of using the sili cone in transformers has been shown in over 20 years of experience in military transformers, in several years of use on the Japanese National Railway, and in a number of power transformers in the Midland, Michigan, area; several other areas around the United States will also test silicone transformers in the next few months.
In addition to these actual applications, which today are well known and have worked out nicely, sup port for the use of a silicone dielectric fluid in power transformers is contained in over 30 years of accumula ted data on dielectric properties and compatibility with the common materials of transformer construction.
The present concern for fire, explosion, health, and environmental hazards are all strong reasons for an evo lutionary approach to using silicones and qualifying them in this application for all major power transformer uses over the next few years.
The silicone liquids of this type are much less
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Ilgmmable than typical mineral oils. They actually have a higher flash point than many PCB-contalning trans former fluids. Although they will burn, they have an extremely low heat of combustion, extremely high flash points and firepoints, and they have been shown in catastrophic testing to be self-extinguishing. They appear to offer a level of fire safety greatly superior to mineral
oils. ' 1 The silicone that we are now recommending, a
dimethyl silicone, has been evaluated by Underwriters Laboratory, and has received an extremely low flamma bility classification number. In Japan and the United States, transformer cases containing PCB's, silicones, and mineral oil ware subjected to catastrophic failure testing. In both tests, all liquids exploded. Most important, fol lowing this test, only the mineral oil continued to burn. Both the polychlorinated biphenyl materials and the sili cone fluid self-extinguished. Normally, in a test of this type you would fuse the circuit cutout. The fault in the silicone fluid self-cleared, thereby extinguishing the arc. With the other materials, the backup fuse blew and ex tinguished the arc.
Following the review of some very extensive dat8 (which Is available to all of you by writing to me at Dow Corning, provided you are willing to put in 4 or 5 hours In reading it), the major insurance companies have given their permission to use silicone fluid in indoor trans formers. Because it is a new material and since no gen eral policy has been established, the insurers have indi cated that they will evaluate each application on an in dividual basis; this is a conservative approach which we highly applaud.
Dow Corning feels that we should look at a .3- to 6-year evolutionary approach of gradually putting a larger and larger number of transformers into operation. We are offering financial inducements to companies who do this in order to collect a large body of cate history data that can be used to convince ourselves and the in dustry that there are no fatal flaws that have been over looked. It's an extremely conservative approach.
Silicones are often used in small concentrations in the preparation of certain foods. Any time you eat a jam or Jelly or drink a glass of some of that good old Milwau kee beer, you are eating a food-grade dimethyl silicone. And if you have an ulcer and you eat Di-Gel, you are also eating it. They are excellent deflaccuants.
The toxicity of dimethyl silicones to mammals, aquatic life, and plants has been very thoroughly investi gated. The extremely low toxicity of silicones has made It difficult to detect any toxic reactions in test subjects. Studies directed toward determining the tendency of sili cone to bioconcentrate have been negative. It has not been possible to date to show that any bioaccumulation
was occurring.
It has been often stated that silicones are persistent In the environment because they do not biodegrade, under the evidence available at the present time. How ever, there is considerable evidence that silicones do chemically degrade in the environment. Contact with soil and water causes the liquid to depolymerize to lowmolecular-weight species, and known chemistry de finitely suggests that these degrade in water or in the atmosphere.
Silicones cost more money than the current liquids being used in transformers, but they are not outrage ously expensive. Referring to the entire market of capacitors and transformers, and making some assump tions which would include the shipment of prosent pro ducts such as PCB's to the manufacturer's site, if we include the shipping costs, my estimate is that the in dustry PCB purchases-would be about $19.2 million.
If good engineering practices are followed to reduce the amount of fluid needed, which has never been a design criteria in the major manufacturer's mind, as mineral oil, of course, is cheap, those costs would prob ably rise with the use of silicone to an industry figure of $25 million.
So the total increased cost to the electrical and electronics market would be about $5.8 million or 29 percent. If we made the assumption that the dielectric fluids cost is 20 percent of the total material cost going into b transformer or capacitor, we are talking about an average cost increase of about 5.8 to 6 percent at the manufacturing level on new equipment.
I feel that this slightly higher initial cost of silicone liquid-filled transformers is more than offset by the cost of monitoring and controlling of PCB-filled transformers over their lifetimes. And with silicone, no known envi ronmental hazards are incurred.
PCB-filled transformers currently In service can be changed over to Q2-1090 transformer liquid without un due problems. I think the work we have done over the past 4 years--some of it In conjunction with Dow Chemical, a lot of it in conjunction with leading trans former manufacturers-shows this.
I think you will be hearing not only from Dow Corning in more detail on this subject. I highly suspect that our worthy competitors, who can manufacture dimethyl silicones to the same specifications once they learn what they are, will go into the market. At that particular time, the law of supply and demand will come into effect. The silicone industry at the present time has more capacity than it can sell. I anticipate the economics will be extremely favorable for further consideration of this product In both transformers and capacitors over the next three years.
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DOW XFS4169L: AN ENVIRONMENTALLY ACCEPTABLE CAPACITOR FLUID
Dean Branson, Ph.D.
Abstract
Dow and McGraw-Edison Companies have devel oped a new capacitor fluid which is electrically, ecologi cally, and economically acceptable. Chemically, the new fluid can be described as buty/ated monochlorodiphenyl oxide.
Dow XFS-4169L capacitor fluid
Dow XFS-4169L capacitor fluid performs equal to or better than Aroclor 1016 in power capacitors. This conclusion is based on dielectric losses, discharge incep tion voltages, capacitor size, fire hazard, reliability, economics, and availability. Dow XFS-4169L capacitor fluid and Its components are acceptable in terms of health and environment according to an assessment of biodegradability, bioconcentration in fish, toxicity to animals, and toxicity to fish. -Other capacitor manufac turers are currently evaluating XFS-4169L for applicabil ity in their respective companies. Field trails have been started with utility companies across the country.
The contents of this presentation represent 4 years of joint research between Dow and McGraw-Edison Company which has culminated in the development of an environmentally and electrically acceptable capacitor fluid.
When PCB's replaced mineral oils some 40 years ego In power capacitors, this represented another step for ward In the electrical Industry's continuing effort to pro vide the public with low-cost electrical power and safer electrical equipment. As a result of the use of PCB's, there has been a downward trend in the cost per kllovar
Capacitor Fluid H.N.E., Projact Manager, Haslth and Envi ronment Research Laboratories, Dow Chemical, Inc., Midland, Michigan.
of power factor correction. In 1971, Monsanto limited the sale of PCB's for
dielectric uses where acceptable alternatives were not yet available. Since then, industry has been searching for alternatives which were ecologically, electrically, and economically acceptable.
Today, we want to report to you that Dow and McGraw-Edison have developed a butylated monochlorodiphenyl oxide known as XFS 4169L. It meets all the above criteria and can be used in high-voltage capacitors.
Initially, over 50 fluids representing several chemical families were selected as possible dielectric fluids on the basis of thdir chemical and physical properties. These fluids were then screened for both electrical perform ance in miniature capacitors and for potential hazard to the health and the environment in a battery of indicative tests.
The conclusion of these screenings was that the most promising chemical family was the alkylated mono chlorodiphenyl oxides.
Electrically, several members of this family per formed equal to or better than Aroclor 1016. It was the health and environmental data that demonstrated the significant advantages of the butylated monochlorodi phenyl oxides.
Electrical Performance
The confidence that McGraw-Edison Company has
in high-voltage capacitors made with the XFS fluid is
based on the following assessment of these six key elec
trical performances.
1. Dielectrical losses. The dielectric losses are as low or
slightly lower than for capacitors with a PCB known as
Aroclor 1016. This is true for both paper-film and all
film high-voltage power capacitors. This means that the
capacitors will operate under normal temperatures and
that the operating costs will be minimal. This is one of
the same significant advantages that PCB's have relative
to mineral oil.
.
2. Discharge inception voltages. Discharge inception
voltage is significantly higher than for Aroclor 1016 in
both paper-film and all-film capacitors. This means that
operating voltages may surge at least 20 to 30 percent
higher without resulting in temporary malfunction due
to electrical discharges known as corona.
3. System size. The size or volume per unit of high-
voltage power capacitor correction known 8S kilovar is
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the tame as for comparative capacitors impregnated with Aroclor 1016. This means that it will not be necessary to redesign capacitors, the capacitor manufacturing, or the
application of capacitors. 4. Fire hazards. As indicated with PCB's, there is a low risk of explosion and fires from power capacitors im pregnated with XFS 4169L. A major problem associated with a failure in a paper-film power capacitor is the decomposition of the paper and, to a lesser degree, the film. The resulting pressure of the gases formed is a major cause of tank rupture. After failure, the flamma bility of the fluid may contribute to a fire only if the paper, the film, and the fluid, are above the ignition or flash temperatures.
Under normal operating conditions, a capacitor will operate between 40 and 80 C. At a time of failure, this temperature will have to exceed the flashpoint of the capacitor fluid before this fluid becomes contributive to the explosiveness or the flammability of the system. In this regard, the flash temperature for the existing dielec tric fluids for mineral oil is 154 C; for Aroclor 1016, 166 C; and for XFS 4169L,174 C. The fire tempera ture for mineral oil, 167 PCB, is greater than 316 C; for XFL 4169L, it is 199 C. This clearly shows that the flash and fire points are substantially above the operat
ing temperatures. The National Electric Code allows the installation of
the electrical devices without a vault if they contain less than 3 gallons of burnable liquid. The most common size of our capacitor used today is a 200-kilovar unit. These units contain less than 3 gallons of fluid, and are in stalled predominantly outdoors. 6. Capacitor reliability. Power capacitors impreg nated with XFS are more reliable than the same type of capacitors impregnated with Aroclor 1016. This con clusion is based on results of comparative evaluations. The following tests have been completed. Three years of accelerated life tests, more than 18 million kilovar hours in full-sized units without failures. Hundreds of sample capacitors operating up to 200 percent of the rated volt ages for a wide range of temperatures, minus 60 to plus
125 C. 6. Economics and availability. The long-range price of power capacitors impregnated with XFS 4169L will be reasonable. The increased price or expense attributed to the fluid is expected to be less than $20 for a 200kilovar unit.
Dow has assured the electrical industry that it will have the manufacturing capabilities to produce XFS at a million pounds per year rate during the first quarter of 1976. Should this fluid prove to be acceptable to the industry, Dow is willing to make the commitment to
produce the fluid in multimillion pound quantities per year by the end of 1976.
Health and Environmental Assessment
The Dow Chemical Company's assessment of the
health and environmental acceptability of XFS 4169L as
a dielectric fluid in capacitors is based on the following
criteria.
"
1. Biodegradability. The components in XFS 4169L
are significantly more biodegradable than the compo
nents of Aroclor 1016. With micro-organisms, the rates
of formation of radioactive carbon dioxide from radio
labeled components of XFS 4169L are much faster than
for 2,5,2' trichloro biphenyl, a major component of Aro
clor 1016. The major component in 4169L is 45 times
more biodegradable than the representative PCB isomer.
This rate of biodegradability is comparable to' several
nonpersistent industrial chemicals.
2. Bioconcentration. The bioconcentration factors in
fish of the components of XFS 4169L are low relative to
the components of Aroclor 1016. The environmentally
significant components in each fluid show a factor 30
times less bioconcentratable in trout muscle for XFS.
3. Toxicity to animals. In both acute and 90-day toxic
ity tests with animals, XFS shows very little toxicity.
For example, in rats, a dose of 10 grams per kilogram of
XFS 4169L was administered orally and had no observ
able effect on rats.
The levels of the components of XFS that accumu
lated in the fat of rats fed the XFS in the diet for 150
days were significantly lower than for the comparable
dietary tests with Aroclor 1016. For example, the accu
mulation in the fat was 22 times less for XFS; the appar
ent plateau level was achieved in 1 to 2 months com
pared to 6 to 7 months for the PCB, and the estimated
half-life of the rat was 7 days with XFS compared to 60
days for the PCB. This indicates the relatively low degree
of toxicity associated with XFS 4169L in animals.
4. Toxicities to fish. The XFS material is only moder
ately toxic to fish compared to capacitor-grade PCB,
which is extremely toxic. The concentration of XFS that
was toxic to fathead minnows was 15 milligrams per liter
compared to 0.76 milligrams per liter of Aroclor 1016,
which is a factor of 20 times less toxic to the fathead
minnow.
'
Dow and McGraw-Edison Companies have deter
mined that XFS 4169L is an acceptable alternative to
capacitor-grade PCB in high-voltage power capacitors.
This is based on the electrical performance and its low potential impact on health and the environment.
Today, McGraw-Edison is proceeding with field
trials of capacitors at utility companies across the
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country. Other U.S. manufacturers of power capacitors are currently evaluating XFS for applicability in their
respective companies.
The information about XFS in this discussion is only a very brief summary of the toxicological and ecological data which have been generated.
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CHLORINATED BIPHENYL DIELECTRICS-- THEIR UTILITY AND POTENTIAL SUBSTITUTES
David Wood*
Abstract
3. We offer an incineration service for liquid PCB
wastes.
,
The paper describes the major reasons for die use of
4. We continue to work with ANSI Committee C107
chlorinated biphenyl In capacitors and transformers.
and other bodies to establish appropriate handling
These lead to establishment of objectives for research
and control procedures for equipment containing
Into potential substitutes. MCS-1238, a non-PCB capaci
chlorinated biphenyl,
tor fluid developed by Monsanto, Is discussed and areas
5. We allocated increased research resources in 1969 to
where further development work is required are Indi
seek 8nd develop effective replacements; this pro
cated. The particular problems associated with definition of "fire resistance" relative to transformer fluids is
gram continues. 6. In seeking possible replacements, we will insure that
raised.
differences between Aroclor and candidate fluids from our program are widely reviewed in order that
I. INTRODUCTION
the potential impact of any compromises is fully
evaluated.
In 1970, Monsanto voluntarily began Its program of
The implementation of these and other programs both
terminating sales of chlorinated biphenyls to open appli
by ourselves and electrical equipment manufacturers was
cations--those which could result in losses to the envi
prompted by the utility of this dielectric family and the
ronment. By late 1972, this program was fully imple
difficulties inherent in developing substitutes to effec
mented end Monsanto was selling these products only to
tively and fully replace it.
manufacturers of sealed electric equipment such as trans
formers and capacitors. Major applications affected by our withdrawal were
carbonless paper, fire-resistant hydraulic fluids, heat
II. UTILITY OF CHLORINATED BIPHENYL IN CAPACITORS
transfer fluids, and plasticizers. Sales for other miscella ' 1. Fire Resistance
neous minor applications were discontinued during the ,
The adoption of chlorinated biphenyls in 1929 as
same period. This action resulted in a reduction of some
capacitor dielectrics stemmed from their superior dielec
45 million pounds per year in the use of chlorinated
tric properties compared to mineral oil. However, recog
biphenyl In areas where entry to the environment was
nition of the fire-resistant character of the fluids influ
less controllable.
enced system 8nd equipment design and standards over
We decided at that time to continue supply to
the subsequent 45 years. It is probably true that today
closed electrical applications because we believed that:
many people find it difficult to assess potential capacitor
1. Entry of chlorinated biphenyl to the environment
fire hazard purely because Aroclor has been used for 45
was limited and controllable:
years.
2. A more biodegradable, lower chlorinated homolog
Particular examples where fire resistance in a
had been developed which the capacitor industry
capacitor is of benefit include:
could use;
a. fluorescent lighting ballasts,
3. Withdrawal would have brought to a halt produc
b. air-conditioner motor capacitors,
tion of equipment essential to the safe and efficient
c. television capacitors,
distribution and use of electrical energy because
d. large power capacitors where high fault currents
' there was no known satisfactory replacement for
can cause rupture and ejection of fluid from
chlorinated biphenyl dielectrics.
pole-mounted units close to people and build
Today we continue to sell chlorinated biphenyl,
ings,
observing the following policy:
e. industrial furnace capacitors.
1. We supply only to manufacturers of sealed electrical
2. Stability
`
equipment such as capacitors and transformers.
The persistence of chlorinated biphenyl in the
2. We supply lower chlorinated homologs, Aroclor
environment is associated with the high degree of ther
1018, to the capacitor industry,
mal, chemical, oxidative, and hydrolytic stability which
Manager, Product and Marketino Dielectrics, Monsanto Industrial Chemicals Company, St. Louis, Missouri.
permits capacitor manufacturers to fulfill the exacting reliability requirements that exist today.
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3. Dielectric Constant/Dielectric Strengths These properties are important in determining the
size of a capacitor, (n a mixed dielectric system, e.g., paper/Aroclor or paper/polypropylene/Aroclor, the dielectric properties of Aroclor permit optimization of stress distribution between the components making up the dielectric layer. This has enabled capacitor manufac turers to reduce paper and film volumes for a given capacitance. I shall discuss under the heading of "poten tial substitutes" the impact that this could have on:
a. paper/film availability and usage; b. design of equipment containing capacitors.
III. UTILITY IN TRANSFORMERS
Chlorinated biphenyl transformers represent less than IB percent of transformers in service. Their use is associated with the need to limit fire hazard in installa tions.
1. Railroad Transformers
Multiple unit cars as used in rapid transit systems have transformers mounted beneath each car. By nature of the type of service, involving high passenger density, safety is essential.
2. Urban Power Substations (e.g., Underground Vaults)
These designs need to take into account city center space limitations and also the safety of the public and maintenance crews. Fire-resistant liquid transformers are helpful to all these objectives.
3. Industrial Load Centers
Efficient system designs for large, power intensive, manufacturing plants (e.g., automotive assembly, steel production) often incorporate transformers close to the electrical load centers. The use of Aroclor transformers at these centers, in the heart of the plants, or overhead in roof structures, protects both employees and plant.
4. Transformer/Rectifiers
Programs to reduce the emission of particulate matter from stack gases, for example in fossil fuel generating plants, include installation of electrostatic precipitators. The transformer/rectifiers energizing the precipitator field must be located close to the electrodes. In many designs, the multiple transformers are located in a penthouse above the precipitator. A fire in the pent house could lead to shutdown of the precipitator, and thus the generating plant, if pollution control is to be
maintained. A fire-resistant fluid is of obvious benefit in this application.
In each of these applications, Aroclor protects the system from:
a. initiation of a transformer fluid fire by sn elec trical fault beneath the liquid level,
b. electrical breakdown of the fluid causing emis sion of flamrjiable gases,
c. propagation of fire if the transformer liquid content is involved in an external fire.
IV. POTENTIAL SUBSTITUTES IN CAPACITORS
1. Research Objectives
In seeking potential substitutes, our research objec tives of necessity involved keeping those properties that gave Aroclor its value. We equally recognized the need that an Aroclor replacement should eliminate environ mental concerns. A replacement should ideally operate across the full range of current Aroclor capacitor appli cations while requiring minimum changes in design of capacitors and equipment utilizing capacitors. - The use of chlorinated biphenyl is worldwide. Monsanto manufactures chlorinated biphenyls both in America and Great Britain. We supply to the capacitor industry of many countries. We sought potential replace ment products that could be made available with the consistent quality control applied to Aroclor on a world wide basis.
We referred earlier to availability of codielectric components in capacitors. A solution requiring substan tial changes in availability of polypropylene film (quantity or quality) or a major increase in short-term availability or capacitor paper, we considered unsatis factory. If in 1974 such increased quantities had been required, they would not have been available. Capacitor production would have fallen short of demand, further jeopardizing efficient power supply.
Our research objectives can be broadly summarized in table 1.
2. Non-PCB Candidates
The capacitor industry is currently examining two Monsanto non-PCB (candidate) dielectrics. These con tain no chlorinated biphenyl and are not chlorinated products. The two fluids are designated MCS 1238 and MCS 1588, Both of these products are blends of syn thetic hydrocarbons with a high dielectric constant additive to give a dielectric constant equivalent to Aroclor 1016. Table 2 lists some of the properties of MCS 1238 and MCS 1588 compared to Aroclor 1016.
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Table 1. Research objectives in seeking potential substitutes for capacitors
1. Match or exceed Aroclor 1016 capability:
a. Dielectric constant - Usage of other components Dielectric strength - Convertability
b. Stability Power factor
- Reliability
c. Fire resistance
- Safety
2. Good environmental compatibility:
3. a. Span existing appli-
.
cations
- Complete solution.
h. Internationally available
- Not solely U.S.A. situation.
Table 2. Some properties of MCST238 and MCS 1588 compared to Aroclor 1016
Property DK 25 C
100 C Corona IV/EVa
Aroclor 1016
' 5.9
4.85
-
MCS 1238
6.0 5.1
-
MCS 1588
6.1
5.1 -
Hydrolysis stability (neutralization number)
Dissipation factor fluid tan 6 60 Hz. 100 C
Dissipation factor model paper capacitor at 90 C
0.00 0.0025 0.0032
0.00 0.05 0.0039
0.00 0.05 0.0035
aSee text explanation, section IV 2.
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Corona inception and extinction voltages are more a function of capacitor design than of the liquid itself. Preliminary industry results demonstrate functioning in capacitors equivalent to Aroclor 1016. Further full-scale work is required before final conclusions can be drawn,
Dielectric constants relate closely to those of Aroclor 1016 over the temperature range of capacitor operation. Hydrolysis stability is mentioned because of work carried out on earlier candidates based on esters, which gave concern because of hydrolysis instability. Hydrolysis was assessed by measuring the neutralization number of a sample with 0.5 percent water added, which had been heated for 168 hours at 210 F in a stainless steel bomb along with an aluminum end a mild steel coupon.
3. Fire Resistance
Neither MCS 1238 or 1588 is fire resistant. This deficiency versus Aroclor 1016 must be closely con sidered.
4. Environmental Considerations
The environmental/health evaluation of capacitor replacement fluids must be related to:
a. Degradation-lf some quantity enters the environment, at what rate and through which mechanism will it degrade?
b. Tissue accumulation c. Toxicity--Occupational safety
Environmental compatability
6. Degradation
Biodegradation has been studied using a semicontinuous activated sludge technique. Forty-eight-hour exposure of Aroclor 1254, Aroclor 1016, and MCS 1238 dielectric fluids to activated sludge using a semicontinu-
ous procedure resulted in the percent biodegradation rates and 95 percent confidence limits shown in table 3.
For the polychlorinated biphenyl (PCB) materials the level of chlorination appears to be the most signifi cant factor in their relative biodegradability. The rate of biodegradation decreases as the number of chlorine atoms per biphenyl molecule increases. Chromatograms representing samples after exposure to activated sludge show significant alteration in the Aroclor 1016 isomer distribution, but little for Aroclor 1254. Degradation of tho nonhalogenated fluid, MCS 1238. proceeds much more rapidly than for the halogcnated PCB fluids with no evidence of resistant components. The methodology for this technique is described in appendix B.
6. Tissue Accumulation
Figuro 1 depicts the results of rat tissue residue level studies vs. time and compares Aroclor 1242, Aroclor 1016, and MCS 1238. A fraction of the ingested Aroclor 1242 and Aroclor 1016 was stored in rats' lipid reser voirs. However, most of this residue was depleted after the rats had been on the basal laboratory diet for several weeks. During the course of the feeding study, residues of Aroclor 1016 accumulated more slowly and to a significantly lesser extent than those of Aroclor 1242. During the recovery period, these PCB residues de creased to lower values for Aroclor 1016.
The residue concentrations of MCS 1238 quickly reached a stable level well below the concentration in the feed. The residues did not increase with continued exposure. After feeding of the treated chow was ceased, the MCS 1238 residues were rapidly metabolized and/or excreted. The tissue residue accumulation and depura tion profile of MCS 1238 shown in figure 1 is markedly different than those of the Aroclor fluids, especially that of Aroclor 1242. Methodology is given in appendix A.
| I
Table 3. Results of biodegradation using a semicontinuous activated sludge technique
Material Aroclor 1254 Aroclor 1016 MCS 1238
48-Hour percent biodegradation
15 + 38
33 i 14 70 + 10
Feed concentration,
PPm
1
1
3
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25 PPM FEED LEVEL FOR RATS
Figure 1. Results of rat tissue residue level studies vs. time, comparing Aroclor 1242, Aroclor 1016
and MCS 1238.
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7. Toxtclty
Before samples of MCS 1238 could be evaluated in the capacitor industry end within Monsanto, acute toxicity data was oathered:
a. Rat-Acute single oral dose LD50: 3,800 mg/kg.
b. Rabbit--Dermal LDjo; 5,000-8,000 mg/kg. c. Rabbit--Potential eye irritation: A slight
degree of irritation resulted when 0.1 ml of undiluted MCS 1238 was placed in the conjunc tival sac of the rabbit eye. The average maxi mum score recorded at one and again at 24 hours after treatment was 12.0 on a scale of 110.0. All eyes had regained normal appearance 72 hours after dosing. d. Rabbit-Potential skin irritation: When un diluted, MCS 1238 was held in continuous 24-hour contact with intact rabbit skin, a moderate degree of irritation resulted. The maximum average score was 3.6 on a scale of
8.0.
Further programs are in process, or scheduled, to study the following:
a. vapor inhalation, b. ultimate degradation, c. 60-day pilot feeding study, d. long-term (2-year) feeding studies, and e. fish tissue residues.
8. Conclusions
To summarize Monsanto research activities:
- A large number of single compounds and mixtures
have been evaluated in terms of physical property
data, environmental compatability, fire resistance,
and model capacitor life testing.
- These have led us to conclude that:
A
a. Aroclor 1016 may well be sufficiently de
gradable to remain in controlled use,
b. MCS 1238 is a potentially acceptable replace ment with the qualification that it is not fire resistant,
- Further programs must be completed with MCS 1238 in order to: a. deepen our knowledge of its environmental compatibility.
b. permit complete evaluation by the capacitor
industry across their range of applications,
c. enable utilities, capacitor users, and agencies to
evaluate the significance of decreased fire resist
ance.
`
As a closing thought to this section, I would like to
comment that since 1929 when Aroclor was tint
developed as a capacitor dielectric, normal commercial
pressures have spurred efforts to find superior replace-
ments. The awareness of environmental accumulation of
chlorinated biphenyls from other applications added
further impetus for more intensive research in the
chemical and electrical industries. Aroclor has defied 45
years of search for a superior replacement.
V. SUBSTITUTE TRANSFORMER FLUIDS
Neither Monsanto nor any other company, to our knowledge, has developed a transformer dielectric with equivalent fire resistance to that of Aroclor. The diffi culties that we face in common with other workers in this field are twofold: 1. Aroclor has become the reference standard for fire resistance in transformers because It works and has "worked for 45 years. To establish standards to guide research effort, there is a need for objective evaluation of the fire hazard associated with the major sectors of transformer use. 2. The chemistry which imparts fire resistance tends also to produce stable molecules. Monsanto seeks replacement products that will provide protection against:
a. fire from transformer faults under the liquid surface,
b. fire from secondary ignition of gaseous arc decomposition products,
c. fire propagation if the transformer is involved in an externally initiated conflagration.
We strive to accomplish this and produce an environmentally compatible product. We have four candidates which are currently being evaluated by the transformer industry. These materials are in a suffi ciently early stage of development that it would be premature to give detailed property data at this meeting.
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APPENDIX A METHODOLOGY FOR FEEDING STUDY
Feeding and Sampling
Rat chow containing 25 ppm Aroclor 1242, Aroclor 1016, or MCB 1238 was prepared by mixing the products into Ralston Purina rat chow. The treated chow was fed ad libitum to adult albino rats for an exposure period of 30 days. Following the 30-day exposure period, all remaining rats were placed on the basal laboratory diet. At predetermined intervals during the exposure and recovery periods, five rats from each exposed set and a control set were sacrificed. Fat tissue was excised for analysis and composited for each group. Samples were quick-frozen and stored in glass containers with aluminum foil-lined caps to minimize risk of contamination.
Isolation
The dielectric fluid residues were isolated from the fat by solvent extraction. A weighed amount of fat was placed in an Erlenmeyer flask and homogenized three times with 25 ml of pesticide-grade hexanes and anhy drous sodium sulfate using an ultrasonic homogenizer. The combined supernatants and washings were filtered through anhydrous sodium sulfate and diluted to .100 ml with hexane.
Lipid Weight Determination
A 6 ml-aliquot of the extract solution was pipetted
into a tared 50-ml beaker. After evaporation of the
solvent under a stream of nitrogen, the beaker and resi
due wore reweighed to obtain the lipid weight of the
aliquot. All residue levels are reported as ppm on a lipid
weight basis.
PCB Cleanup And Measurement
,
Sample cleanup for the extracts containing Aroclor 1242 and Aroclor 1016 residues was accomplished by
pipetting an aliquot of the extract onto a 5 percent deactivated alumina column and eluting with 125 ml of hexanes. The column eluate was collected in a KudernaDanish evaporative concentrator, a 3-ball Snyder condenser was attached, and the solution was concen trated to 5 ml. The residue levels in the extracts were measured by gas chromatography using an electron capture detector.
Non-PCB Cleanup And Measurement
Sample cleanup for the extracts containing MCS
1238 residues required separation of the residues from
the lipid by preparative scale get permeation chromatog
raphy. Following the GPC separation, the extracts were
further cleaned up on an alumina column, collected, and
concentrated as above. The residue levels in these
extracts were measured by gas chromatography using a
flame ionization detector.
.
Calculations
Calibration curves for each product were prepared by plotting detector response (total peak area) versus nanograms of standard injected. Residue levels in the samples were determined by summation of the total area of peaks corresponding to peaks in the standard and use of the appropriate calibration curve. The calculations were done as follows:
(N)(VF) Rosidue (ppm) -----------
(V,)(W)
where N * Amount of product from calibration curve (ng),
Vp = Volume of final concentrate (ml), V| E Volume injected (ul), W *= Lipid weight of original sample (g).
APPENDIX B
.
TECHNIQUE FOR BIODEGRADATION METHOD
Biodegradation Method
Since activated sludge is one of the most important agents for sewage treatment, test procedures evaluating its action are of great importance.
The semicontinuous activated sludge (SCAS) method has been extensively utilized in the development of biodegradable detergents. In our SCAS procedure, patterned after the Soap and Detergents Association's
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standard method (1,2) mixed liquor (activated sludge and supernatant) from a local domestic sewage treat ment plant is charged to magnetically stirred glass vessels of t.5-1 capacity. Means for aeration and sampling are provided. The SCAS unit is generally operated using a retention or aeration time cycle of 24 to 72 hours. At the beginning of each cycle, synthetic sewage (300 mg glucose, 200 mg nutrient broth, and 130 mg K3HPO4) and the appropriate test material in ethanol solution are added to the mixed liquor (2,600 mg/I suspended solids concentration). Aeration is maintained until the end of the cycle, at which time the sludge is settled and 1 I of supernatant drained. The cycle is then reinitiated by the addition of tap water, synthetic sewage, and test mate rial. Operation of the units can be continued for an indefinite period of time until consistent degradation rates are observed.
Sample Analysis
Biodegradation of the test material was determined during one cycle each week by analyzing 20 to 50 ml mixed liquor samples withdrawn after feeding and at the
end of the aeration cycle. The mixed liquor analytical procedure involved extraction with three successive 26-ml portions of hexane, and drying combined extracts with anhydrous sodium sulfate. Extracts were concen trated in a Kuderna-Danish evaporative concentrator equipped with a 3-ball Snyder condenser, and measured by electron capture or flame ionization gas chromatography. Calibration curvet for each product were pre pared by plotting detector response (total peak area) versus nanograms of standard injected.
The percent biodegradation was calculated from the following equation:
percent biodegradation = (CQ - Cn)/C0 x 100
where CQ and Cn use the initial and final concentration of test material, respectively, on the mixed liquor.
REFERENCES
1. J. Am. Oil Chem. Soc., Vol. 42 (1965), p. 986. 2. J. Am. Oil Chem. Soc., Vol. 46 (1969), p. 432.
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SOME COMMENTS ON ALTERNATIVES TO PCB's Bruno Rey Coquais*
Abstract
In the transformer industry, the benefit of a non flammable liquid seems to exceed the risks of pollution by polychlorinated biphenyls; however, to minimize eventual contamination of the environment, it is suggest ed to use, when possible, e mixture of chlorobenzene end trichlorobiphenyl or even chlorobenzene alone.
For the impregnation of capacitors, most of the subttitutes which can be Imagined are not very attractive, though they ere useful for certain applications. It is pro posed to use a mixture of pure dichlorobiphenyls and their alkylated derivatives. This impregnant, named chloralkylene, has dielectric properties very similar to the Industrial trichlorobiphenyl.
The tests In progress already show that chloralkyhne is easily biodegradable and has a low toxicity. This compound seems to be quite acceptable for the environ ment and should be a perfect substitute for polychlori nated biphenyls In capacitors.
To begin with, I would insist on the fact that heavy chlorinated biphenyls have been used for a long time in dispersive applications as plasticizers and for other uses. Although these types of applications have been stopped in accordance with the OECD recommendations of the February 14, 1973, It is not surprising to continue to find these persistent, highly chlorinated PCB's every where In the environment. It is therefore very difficult' to know if the electrical uses of PCB's for transformers and for capacitors have a significant contribution to the pollution of our environment.
TRANSFORMERS
PCB's are used in transformers only when the fire hazard is high (department stores, theatres, movies, skyscrapers, factories); otherwise oilfilled transformers, which are cheaper, are always preferred. We do not think dry-type transformers would be a competitive alternative in spite of the fact that silicone and epoxy belong to the range of products we market. They may be very attrac tive in some cases, but in addition to certain economical and technical disadvantages, dry transformers do not offer a perfectly safe solution wherever flammable va pors (solvents, oil, gas) may be present accidentally.
We believe a nonflammable dielectric liquid is abso
* Development Manager, Prodetec, S.A., 26 Quel Peul Doomer, Courbovolo, France.
lutely necessary to prevent the risk of fire in transform ers. In table 1 we have listed the different possible solu tions. In the United States, at this lime, transformers are filled with Incrteen 70-30, which is based on pentachlorobiphenyl, or with Inertecn 100-42. To minimize the pollution risk, a mixture of trichlorobiphenyl and chlor obenzene or even the chlorobenzene alone could be used in spite of some technological problems.
In any case, the systematic recovery of used PCB's will further limit pollution hazards; our company Prodelec has organized this practice throughout France since 1968, as soon as this pollution problem became known. This systematic recovery has now been enforced in France by the French law of July 8, 1975, on PCB's.
CAPACITORS
For capacitor impregnation, we have examined vari ous possible solutions. We think that the performances of such compounds as silicone; sulfone or synthetic oil (alkylbenzene, polybutene); phthalate; and sebacatewhich we are indeed selling ourselves for certain applications-are not really satisfactory enough for generalized or widespread use.
In our opinion, a substitute to PCB's should be char acterized by:
High permittivity; Nonflammability, at least not sustaining com
bustion; Compatibility with polypropylene film; " Being a permanent liquid with no crystalliza
tion until -25"; Good thermal and electric subfield stability; Regarding its effect on the environment, being
fairly easily biodegradable, to eliminate the risk of accumulation, and by having low toxicity. To get a good and nonflammable dielectric fluid means in practice that the compound must be a chlori nated aromatic hydrocarbon. We have studied, tor in stance, new structures, as shown in figure 1. With chlorobiphenyl oxide, we are afraid of the risk of metabolization in highly toxic dioxins and we feel that products of the family of the chlorobiphenylethane are technically and environmentally much more promising. Actually, in troducing a totally new compound would require a long and expensive testing program and it seems better to take advantage of the huge amount of knowledge gather ed about PCB's and to see how it may be possible to improve the present situation.
325
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Table 1. Possible solutions for dielectric liqoid
IEC Chloro- Chloro Pour Viscosity e Hydrogen Askarels
type biphenyl benzene Point
(C)
Cst at 20 C
at 20 C
index3
for transfor
mer
T1 60% hexa 40% tri <-33
21
TZ 45% hexa 55% tri <-40 and tetra
70% penta 30% tri <-30
11 20
4.5 <0 Pyralene excess Cl T-j Pyro-
clor
5 <0 excess Cl
5 0 Inerteen 70-30 Pyralene
T4
45% penta . 55% tri and tetra
T3 100% tri
<-40 <-18
10 65
60% tri 40% tri <-50
7
40% tri
60% tri and tetra
100% tri and tetra .
<-20
Chrystallize
-9
<0 Pyralene excess Cl T2
6 16 Pyralene T^ Inerteen 100 42
6 10 Pyralene 1460
4
6 <0 excess Cl
'Hydrogen index
No. hydrogen - No. chlorine
Molecular weight
'
!
i
326 NEV 026171
^39426 WATER PCB-SD0000056913
CL CL
E=4.
FLASHPOINT FI REPOINT
Chfons (Sipfwrylozid^
103 C 17! C
Mttobolism
Chkxodkjjsires
Cl
0 0
Cl
(developed by Telgin)
ci
CH
I ch3
C!
* 5.6 FLASHPOINT
FIREPOINT
180 C 250 C
NEV 0 2 6 1 7 2
Figure 1. New structures for nonflammable dielectric fluids. WATER PCB-SD0000056914
O Cl
dichloro blp^*Ayl
2--2* 2 -V
Wz CM -CHj
Figure 2. Structure of chloralkylene.
CM, CH-
Table 2. Composition of various impregnants
Chloralkylene
Composition, percent
12
Biphenyl Monochlorobiphenyl Dichlorobiphenyl Trichiorobiphenyl
Tetrachlorobiphenyl Pentachlorobiphenyl A1 kyl chi orobiphenyl
isomers Chlorine content, percent
*0 0'
20 0 0 0 80
25.8
Pyralene 3010
(trichlorobiphenyl)
Pyralene 1500
Pyralene 2000
0 0 1.6
0 0.5 18.4
11.4 37.5 44.0
57.1
40.0
23.4
29.4 20.5 11.7
2.2 1.5 0.9
- -
42. 38.5 33.5
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Table 3. Comparison of chloralkylene to commercial trichlorobiphenyls
Characteristics
Chloralkylene 12
Pyralene 3010 (trichlorodiphenyl)
Specific gravity at 20 C 100 C
Coefficient of expansion
Viscosity Cst. at 20 C 100 C
Pour point (ASTM D 97)
Firepoint (Cleveland)
Permitivity at 20 C 100 C
Resistivity 100 C - 500 V - 1 mn
Dissipation factor +g6 100 C - 50 cps
1.163 1.097 7.5 x 10"4
135 3.2
-25 C 258 C
6.00 4.86
>3000 x ,10Q
<0.02
1.391 1.319 6.8 x 10"4
65 2.3 -23 C
none until boiling
' 5.93 4.80
9 >3000 x 10
<0.02
DCCHETK5H (prant)
Figure 3. Excretion by rats, with diet of 2 ppm/day for 5 weeks.
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/ /
Figure 4. Excretion by rhesus monkey; single oral dose 1 mg/kg.
The studies carried on, in particular by Prof. Korte and Dr. Klein in Germany, teem to prove the easy biodegradabllity of PCB's when they have a very low chlorine content; therefore, pure mono- or dichlorobiphenyls could be quite acceptable for the environment.
As an Impregnant consisting only of mono- and dichlorobiphenyls would crystallize at room tempera ture, It Is necessary to produce a more complicated mix ture to get a permanent liquid at ell temperatures. We have therefore developed a product named "chloralkylene," obtained by addition of an alkyl chain, actually an isopropyl group, on a mixture of nearly pure dichlorobiphenyl isomers (figure 2).
As shown on table 2, chloralkylene contains .no penta- nor tetrachlorobiphenyl and the trichlorobiphenyl content can be extremely low. Technically, for Its dielectric and physical properties, the chloralkylene is a perfect substitute to the commercial trichlorobiphenyls (Pyraiene 3010, Arochlor 1016), as shown in table 3 and as checked bv some major capacitor manufacturers here
and abroad. To assess Its impact on the environment, we have
given chloralkylene to the Institute for Ecological Chem istry in Bonn, Germany, Prof. Korte. This institute is engaged in an extensive investigation on "PCB's in the Environment." We therefore hope to have next spring the final results on the fete of chloralkylene In compari son with PCB isomers.
Tests on environmental acceptability are actually being carried out with chloralkylene based on 2-4* dichlorobiphenyl labeled with 14c. The tests consist of a study of the balance of the excretion, the storage, and the metabolism in rats and in monkeys (figures 3 and 4); the monkey studies are being completed at the Institute of Experimental Pathology and Toxicology, Albany Medi cal College, Albany, New York. These tests also examine the fate of chloralkylene in a soil plant ecosystem and in an aquatic ecosystem, as well as its behavior under atmosphoric conditions, upon waste composting, and in sewage treatments. The results so far obtained prove that
330 NEV 026175
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chloralkylene does not accumulate, It metabolized quickly, end behaves generally like the dichlorobiphenyls isomers themselves.-
Chloralkylene is two times less toxic than trichlorobiphenyl when one compares the acute toxicity values. At this time, there is no real reason to consider PCB's dangerous for the labor manufacturing capacitors, If the necessary precautions are taken. We think that with an easily biodegradable compound such as chloralkylene, longterm effects due to accumulation along the food
chain do not need to be feared.
'
The chloralkylene price is presently twice that of
the currently commercially available polychlorobiphen-
yls, which would result in an increase of the capacitor
costs of about 6/10 percent. However, by substituting
mineral oil or other substitutes with less outstanding
characteristics, the increase of the cost of capacitors
would be much higher. We hope to-improve its economy
and are quite confident that chloralkylene could thus be
an excellent substitute for trichlorobiphenyls.
331 NEV 026176
739431 WATER PCB-SD0000056918
PCB's AND THEIR SUBSTITUTES - A BRIEF LOOK AT SOME EXAMPLES OF PAST TRADEOFFS
Dale Hattis, Ph.D., and Albert Murray, Ph.D.*
Abstract
Some aspects ere described of a study of the economic, health, legal, and other impacts of the past voluntary restriction on PCS sales. Examples illustrate the importance of examining the effects of substitute technologies in assessing regulatory policy by showing the potential for surprises in this regard. In the PCB case, substitutes may be producing both unanticipated economic benefits and unappreciated health and safety risks.
I am Dale Hattis of tho Center for Policy Alterna tives at M.l.T. My colleague at the center, Dr. Albert Murray, who was originally scheduled to speak here-and who would be the most appropriate speaker on this subject-was unfortunately taken ill about a week and a half ago and he is now still recuperating in the hospital. What I have done in his place for presentation today is to extract some particular examples of tradeoffs from Al's work on PCB's, which illustrate some occasionally surprising features of the technological changes that arise out of environmental/health concerns.
For context, I would like to say that our project, sponsored by tho Council on Environmental Quality and EPA, and under the direction of Dr. Nicholas A. Ashford, has for the past year been exploring ways to analyze the economic, environmental health, legal, and other impacts of regulatory decisions related to environ mental chemicals. In this exploration, we are now in the process of completing eight experiments in the analysis of the impacts of particular regulatory actions, primarily drawn from the past 5 years of history. The first of our eight experiments, though not strictly resulting from a mandatory governmental action, was the restriction a few years ago of the sale of PCB's for particular uses. Because our case studies are experiments to explore the practical use of methods, and because the resources we could devote to each case were relatively small, we could not perform as comprehensive an elucidation of effects as we would have wished. Nevertheless, we do think that our analyses have revealed important types of questions, similar to those referred to yesterday by Mr. Train, which are difficult to deal with in the single chemical
"Research Associates, Center for Policy Alternatives, Massachusetts Institute of Technology. Cambridge, Massachu setts.
reactive context of most current regulatory authorities My initial two examples of such questions on PCB's
illustrate the fact that it is sometimes difficult to be sure that technological changes introduced with the intent of reducing environmental health risks accomplish their purpose on balance, when the risks of substitute prac tices Bre considered. Sometimes there appear to be legiti mate reasons for concern that particular changesespecially in the absence of continuing regulatory followup-might create environmental health hazards as dangerous or more dangerous than the ones that are eliminated.
As a first example, the substitutes for PCB's in some large heat exchangers and in some special hydraulic fluids for high-fire-risk uses are flammable at elevated temperatures. Concern for the lack of fire protection previously provided by PCB's in these situations has reportedly caused a substantial increase, as much as a doubling in some cases, in fire insurance rates on some industrial facilities employing high-temperature heat exchangers. In our case study, Al Murray estimated the total increase in premiums at possibly in the tens of millions of dollars annually. This, of course, reflects mainly property damage and not the human cost. How ever, if our information on the increased premiums is correct, and if the apparent perception of the insurance companies is correct as to the size of the added chance of catastrophic fires, then we must consider that such events would be likely to be accompanied by appreciable human casualties. The rise in insurance rates, of course, may not reflect an actual change in risk, and in that case the increased insurance cost is simply a transfer payment to the benefit of the insurance companies, but the mat ter seems to deserve further exploration with the aid of hard statistics on actual fire-risk experience. If the data confirm that appreciable human impact may be ex pected to occur, alternative means for reducing this risk might be productively evaluated.
Another, although probably less important, example of potential risk of substitute technology arises in the case of the former use of PCB's as a dye-solvent for caibonless carbon paper. It may be recalled that at some frequency PCB's from this source found their way into recycled paperboard products for food contact use, and this was a source of concern for the FDA. Now the PCB's formerly used for this purpose have been replaced, but unfortunately it is not public information what exactly has replaced them. The barrier of trade secrecy
332 NEV 026177
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in this instance, as in many others, can frustrate attampts to assess the `dilference in environmental health risk produced by the change in technology.
Two other examples illustrate the potential (or a different category of surprises--those in the economic
area. Formerly, PCB's costing on the order of 25 cents
per pound wore used in many paints and coatings, some times as a major ingredient. In this application PCB's were a chemically stable blender and conferred resist ance to fire, impacts, water, and weathering. Our inquir ies with paint manufacturers indicate that chlorinated paraffins now perform essentially all the technical func tions of PCB's at about half the former cost. Our industry informants mention some increased problems in a few of their products with lowered stability to dechlo rination-causing occasional discoloration and loss of weathering resistance-but over the great bulk of their product lines, the industry perception appears to be that the change has been economically beneficial. PCB's had evidently become established as paint additives before the availability and advantages of the chlorinated paraffins became widely appreciated. Later, when approximate technical equality and lower prices might have tempted paint manufacturers to substitute, the usual inertial resistance to any change appears to have caused this opportunity to be generally neglected. The real world and the economists' ideal one occasionally
behave differently. Another example of a surprise {at least to us) in the
economic area is the potential importance of even small adverse impacts on sport fishing. A U.S. Department of Interior survey {ref. 1) indicates that in 1070 a total of about 700 million person-days and five billion dollars were spent in pursuit of this pastime -- mainly in fresh water. The five billion dollars must, of course, be con sidered an underestimate of the actual "value" of that activity to people. If PCB's had continued to be used as they were in the past, wc might speculate that additional concern of people about residues (such as that now publicly in evidence), or possibly some declines in fish populations might have led to small fractional declines in participation or enjoyment of fishing by some portion of the population. If this were to occur, the loss of value to society of even less than a fraction of a percent of national sport fishing activities might be appraised at tens of millions of dollars annually--depending on the "vBlue" realized by former fishers in substitute recrea tional activities. .
The importance of examining subtle and uncertain effects, including the effects of substitute technologies, is illustrated by such occasional insights into their poten tial magnitude.
REFERENCES
1, Fish and Wildlife Service, Bureau of Sport Fisheries, U.S. Dept. Interior, "National Survey of Fishing and Hunting," Resource Publication 95, GPO, Washing ton, D.C., 1972.
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ENJ-2065--AN ELECTRICAL INSULATING FLUID E. J. Inchalik, Ph.D.
Abstract
.'
The need for an electrical insulating fluid whose use would avoid the adverse toxicological and ecological effects associated with polychlorinated biphenyls prompted a study of organic esters as possible substi tutes, The study culminated In the Identification of dilsononyl phthalate (ENJ-2065) as a dielectric fluid of potential interest to the capacitor industry. ENJ-2065 has been made available to that industry and it is now being used In some commercial capacitors.
In late 1970, a study was begun at Exxon Research and Engineering Company by Drs. A. J. Rutkowski and E. O. Forster to develop an electrical insulating fluid whose use would avoid the adverse toxicological and ecological effects associated with polychlorinated bi phenyls. This study culminated in the identification of diisononyl phthalate (ENJ-2065) as a dielectric fluid of potential interest to the capacitor industry. Exxon Chemical Company U.S.A. has made ENJ-2065 available to the industry for its evaluation and it is now being used in some commercial capacitors.
In the preliminary phases of this study, the dielec tric properties of a significant number of mono- and dibasic acid esters were determined in order to obtain a general understanding of the interrelation between mo lecular structure and dielectric properties. From these data it was concluded that major attention ought to be directed at the esters of phthalic acid. The phthalates that we tested all had dielectric constants of 4-6, close enough to the desired level for fluids for tjie widely used paper-based capacitors to justify further evaluation. The optimum dielectric constant for these capacitor fluids is one which closely matches the dielectric constant of the paper. A close match reduces electric field inhomogeneitias, increases dielectric strength and lifetime, and de creases capacitor size. Other important property criteria for a paper dielectric fluid include a low dissipation fac tor, to reduce energy loss and destructive heat buildup; a high dielectric strength, to reduce capacitor size and im prove service life by permitting short-term exposure of the fluid to abnormally high stresses without break down; a low gassing tendency, to avoid production of gases that could lead to pressure buildup in sealed units; stability at elevated temperatures, to prevent capacitor
"Research Associate, Chemical Intermediates Technoloov Division ot Exxon Chemical Company, Linden, New Jersey.
breakdown and stabilize performance; low viscosity to allow for easier impregnation and filling of capacitors and elimination of air pockets; a low order of toxicity and compatibility with the environment.
Consideration of these factors as well as availability and cost resulted in narrowing the choice of potential candidates to those shown in table 1. From this list, diisononyl phthalate (ENJ-2065) was selected as the most promising for additional study. ENJ-2065 was cho sen on the basis that it has (1) a higher dielectric con stant than the phthalates of higher molecular weight. (2) an advantage in its loss characteristics relative to the lower molecular weight dihexyl and dioctyl phthalates, (3) a relatively high flash point of 430 F, (4) a mote highly branched molecular structure than dihexyl and dioctyl phthalates with the potential for improved hydrolytic stability and (5) a good balance of other physical and electrical properties. ENJ-2065 is manufac tured in the United States by Exxon Chemical Company U.S.A. from phthalic anhydride and a mixture of branched isomeric alcohols in which C9 alcohols pre dominate.
Electrical insulating fluids have to remain essentially unchanged chemically when subjected to temperature cycles. Once having chosen ENJ-2065 for further evalua tion, it was desirable to know what effect certain con taminants might have on its stability, how these contam inants might be removed, and what additives, if any, might be useful in enhancing its stability.
The effects of small amounts of two potential con taminants, alcohol and water, on conductivity of ENJ-2065 are shown in tables 2 and 3. The results show that alcohol levels of less than about 1,000 ppm and water levels of less than about 100 ppm can probably be tolerated without affecting performance seriously. To re move small quantities of these impurities as well as any acids or catalyst residues from the production of ENJ-2065, we found percolation through a packed col umn of activated Attapulgus clay to be effective, but we did not carry out extensive studies to optimize a purifi cation system. It is ouf feeling that systems now being used in the industry for purification of PCB's prior to use in capacitors, or slight modifications of them, will prove to be satisfactory for ENJ-2065.
Although the most widely used capacitors today are of the 8tl-paper type, newer types based on polypropy lene film and paper or on all-polypropylene film are growing in importance. With capacitors of this type, the dielectric constant of the fluid is less important.
334 NtV 026179
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Table 1. Electrical and physical properties of phthalate esters
Phthalate '
Dim
Ester
D1hexyl ethyl hexyl Diisooctyl ENJ-2065 Diisodecyl Ditridecyl
Dielectric constant 5.64
Tan delta
--
AC conduc tivity,
10"11
(ohm-cm)"^ 9.0
Breakdown voltage (KV/0.1 in.)
Bolling
po1nt---mi d1
@ 5 nwHg, C
210
Pour point, C -33
Viscosity, cps., 20 C 50
Flashpoint,
COC, F
380
Firepoint, COC, F
420
5.33 0.14
2.1
28
230 -50
81 425 475
4.97 4.66 4.45 0.30 0.05 0.02
1.3 0.29 0.20
27 30 36
235 252 256 -45 -48 -50
83 95 no
430 430 452 485 495 515
4.08 0.01
0.04
29
286 -37 230 470 555
335 NEV 026180
739435 WATER PCB-SD0000056922
Table 2. Effect of residual alcohol on conductivity of ENJ-2065
Temperature cycle (1,000 V, 60 Hz)
Conductivity (10-1^ ohm-cm) Wt. percent alcohol added 0 0.01 ' 07T
t\> o Oo
oo
25 C
0.78 40 3
1.97 65 4
1.98 320
12
Table 3. Effect of residual water on conductivity of ENJ-2065
Temperature cycle (1,000 V, 60 Hz)
Conductivity (10 IP ohm-cm)-1
Wt. percent water added 0 0.001 0.01 0.1
25 C 90 C 25 C
0.78 40 3
2.7 165
10
3.7 135 >400 >400
25 70
Table 4. Weight gain of PP film in contact with dielectric fluid
Fluid
Run number 1 23
ENJ-2065
Arochlor 1242
11.0 10.9 13.8 18.8 18.2 22.8
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Impregnation of the polypropylene film with the fluid, however, is of great importance and prompted a brief ttudy, summarized on table These data show that ENJ-2065 swells polypropylene capacitor-grade films satisfactorily, as measured by the film weight gain after 2 days at 60 C, so that film impregnation should not be a serious problem. The next generation of capacitors
may well be based on metallized polypropylene film.
Polychlorinated biphenyls cannot be used for this type
of capacitor since they generate hydrogen chloride,
which can lead to premature breakdown.
In summary, we believe that ENJ-2065 has a bal
ance of properties such that it will find a niche in the
capacitor fluid field.
,,
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GENERAL DISCUSSION OF SESSION V
CHAIRMAN MUIR: All right. I tee that we have reached our scheduled departure hour. I think it's only fair to entertain a few questions from the audience and given the diversity, I would request that people raise a question from the floor and then address their questions to the individual they would like an
answer from. MR. BEN KININGHAM (Illinois Lung Association,
Springfield, Illinois): I do not have any particular gentleman on the panel to address. I just want to refer to the breakdown of the film, if anyone could elaborate on how that comes about, and if so, it there any research that is being carried on now in development of films that would be any more stable. MR. RICHARD ROLLINS (Jfird Corporation, Benning ton, Vermont): Are you talking about a biological breakdown? MR. KININGHAM: Biological or chemical or both
breakdowns. MR. ROLLINS: It is a reduction type atmosphere in the
capacitor so it does not see the oxygen that would normally be considered. The basic problem Is not one of the degradation as much as it is an inherent characteristic of not being able to survive voltage levols or stresses in an AC application. MR. KININGHAM: Would it be feasible to develop an alternative program? MR. ROLLINS: The organic type films have been used or have been attempted to be used in AC capacitors. The basic problem is one of corona exception and corona distinction voltages, and this is inherently low and goes down to initiation of points 250 to 275 volts and the extinction voltage is extremely low. The meaning of the corona is that the capacitor slowly deteriorates by this ionic device which is the definition of corona. The interpretations of corona I am not going to get into today because every capacitor designer has his own opinion, but every capacitor designer is completely aware of what the corona problems can do. So essentially what we are saying is that organic films have the basic problem of hot being able to withstand high AC voltages, especially in the dry system.
On an impregnated system, the circumstances are still there, so you are not really changing the circumstances a great deal in all polypropylene film or any organic film when you impregnate it. VOICE: I have a question for Dave Wood. We heard a
number of things about environmental factors. How about a still lower chlorinated material than 1016 that might be a more desirable material? I believe Monsanto has passed a given developmental material such as 1043, which Is a lower chlorinated material, MR. DAVID WOOD (Monsanto Industrial Chemicals Company, St. Louis, Missouri): We have done considerable work with MCS 1043, but at the present time commercialization of such a product must hang in the balance pending further conclu' sions being drawn about the true significance in the differences observed between the trichlorinated materials and bichlorinated materials. Aroclor 1016 was itself a reduction in materials from the Aroctor 1042 widely used by the industry.
In order to carry through development of the dichlorinated material, I think we need some approvals from the community that they recognize a movement in that direction as one that should be taken.
So yes, some data are already available. Acceler ation or stopping of that program depends largely, on some of the things that we hope will come out of this conference this week. MS. NANCY STROUP (Environmental Defense Founda tion, Washington, D.C.): I apologize for the openhandedness of my question, but I hope that the panel members will respond as concisely as possible.
One of the speakers mentioned that his concern was that we not jump from the frying pan into the fire, and I am sure it's the concern of everyone at this meeting. To that end I would like to know when the four or five compounds that are now being developed to replace PCB's will be tested for the health and safety of these compounds, including carcinogenic, immunogenic, and teratogenic tests before your marketing. And whether this informa tion will be available for independent review. DR. MUIR: Essentially, as I already outlined in my talk, we developed a date for the work and the work is going forward and we recognize the biphenyl prob lem and that replacing the product inevitably is going to have to satisfy the most thorough and rigorous testing. DR. DEAN BRANSON (Dow Chemical, Inc., Midland, Michigan): In the case of methosilicones additional data will be published very shortly and will be publicly available. I think this is most in the minds of all manufacturers when they consider substitutes
NEV 026183 338
739438 WATER PCB-SD0000056925
(or the material which is dielectrically one of the
best ever developed. This will seem to solve the
problem when it comes out.
DR. E, J. INCHALIK (Exxon Chemical Company,
Linden, New Jersey): A great deal of information is
alieady available. You may recall in 1972 a program
sponsored by the National Foundation of Health
Sciences and one subject made by Dr. Tapper, what he observed at comparison of PCB and mercury, it
was like an ideology searching for a disease, and
that's a quote.
The recent study by Dr. Hartung of the
Univetsity of Michigan has concluded that no prob
lems attributable to polyesters have been noted due
to the constant low level exposure of the general
population, and that occupationally, only ntild skin
irritation has been observed at high exposures. But
he did point out that ecological work should be
continued. And I might add that Dr. Tapper sug
gested the same.
To help answer those questions, particularly
related to these items, a research grant has been
made by the University of Missouri to the Manufac
turing Chemists Association, and they are starting
tests. 1 think we can hope within the next year or so
results will be coming from this study obviously
available to all which will help answer these ques
tions.
MR. DUNCAN MacARUTHUR (Booze Allen and
Hamilton, Inc., New York, New York): Well, some
of the things that you have asked for are in progress
and when these things are available, they will also be
made available to the general public.
MR. DAVID C. MORRIS (Weyerhauser Company,
Tacoma,-Washington): You stated, sir, that a cost
of $4.9 million would be necessary for I guess you
would call them secondary market users like my
company, to replace our PCB with some substitute.
Did I understand you correctly, Mr. Mac-
Arthur?
MR.MacARTHUR: Yes.
MR. MOSS: Just for my own sake, I just believe in it
very strongly, the cost alone is estimated at $2
million and we are right in the midst of investing.
And I think somewhere along the line the investing
might not take into account the factors that we
initially have to face. I would guess it's at least 50
times over.
CHAIRMAN MUIR: Yes, sir.
.
VOICE: There are three experimental items coming on
the market. Will someone label these transformers-
MR. ROLLINS: Well, I'm not too sure, but there have
been requests that major capacitors manufacturers
now conform by labeling all capacitors that have greater than I believe 5 pounds of Aroclur--I may be wrong, but on small capacitors, the basic problem is the label gets hidden because this is placed into another piece of equipment. MR, STEVE NUMUS (Environmental Protection Agency): I have a question for Richard Mont gomery regarding the use of silicone which was approved by Underwriters Lab for indoor use. Do
you know the reasons why it was approved for indoor use and why it was not approved for outdoor use?
And secondly, can somebody give me an idea of the percent of transformers in the United States used for outdoor purposes as opposed to indoor purposes? MR. RICHARD H.- MONTGOMERY (Dow Corning Corporation, Midland, Michigan): First of all, Underwriters Laboratory does not approve of any particular material for any given use-once you exceed 600 volts in a transformer, Underwriter's Laboratories has no certification. The only certifica tion received from Underwriters' Laboratories is as to the fire hazard of your particular material on a scale which ranges from 0 to 100, with the burnability of water as 0, and gasoline as 100. Therefore, Underwriter's Laboratory does not approve silicone material for indoor use.
In respect to the use of dielectric fluids in transformers, the electric code for outdoor uses does not specify nonflammable material. It does in subsection 450, paragraph 23 approve the use for the indoors. These are the only materials approved for use. MR. NUMUS: I want to know the percentage as opposed to indoor use. MR. MONTGOMERY: Well, my research seems to indicate 85 to 90 percent of the transformers sold in the United States are currently outdoor applica tions, and the other 10 to 15 percent are indoor applications, for safety is of paramount importance, MR. WOOD: Essentially the figure that ho is using is pretty accurate. Very large power transformers are filled with mineral oil because, if they're out in the field, there is not a substantial hazard, they can be screened out. In the medium voltage range the use of askarel is something under 15 percent of the transfgrmers used in that medium voltage area. MR. CLIFFORD H. TUTTLE (Aerovox Industries, Inc., New Bedford, Massachusetts): I really have two questions--another alternative mentioned up there, the capacitor for getting the high voltage can consume 20 to 50 million pounds a year. How long
NEV 026184
739439 WATER PCB-SD0000056926
would it take fluid to be available in that type of quantity; 1 year, 2 years, 3 years, or what? I don't want to pressure you, I just want to determine.
The second question is a third of that market is lighting, fluorescence. If you have an application at 100 C, are any of these fluids or alternatives capa ble of operating at that temperature without break
ing? MR. MONTGOMERY: Let me answer your second
question first. The answer is yes. The answer to the first question is we do have the productive capabili ties capable to handle that market. It could be
accomplished very quickly. It would probably be faster than the industry takes to evaluate and qualify new mateiial. MR . WOOD: In terms of Monsanto, alternatives could be made available on a prqduction basis in calendar year 1976, in relationship to the stability of these materials at 100 in the HIB and the fluorescent lighting capacitors, thSsc are test sequences which arc going on under our test programs. And the results will be forthcoming. We are in a period now of collective work. We are not ready to go tomor row.
340 NEV 026185 739440
WATER PCB-SD0000056927
\V_'ASU><w To (iivv4 C'l'o/.t (.O'Pp) I Ixi'i Ci'-C.
1. SCOPE
.
Shis standard establishes guidelines for the
sasa transport, us.,, l*. ..s. ce.*.,nGQ , .^.d dis
posal of askarol and asfcarol-coakcd material
used la capacitors and transformers.
2 . CiM4WiXt in .' O.wOfc^
2.1 G.-.rr.ral. Vho tern "askarol" generally
describes a broad class of nonflammablo
synthetic chlorinated hydrocarbon.insulat
ing1 liquids widely used in capacitors,
^^rc*<rw to0^ric-aT^ /
# w*c* wCccggo^Tj^
equipment operated at power frequencies,
Askurels consisting of or containing
polychlorinated biphenyls (PCSs ) have boon
used in many applications since the oarly
1520's, but-'only recently waa it dis
covered that ?CBa arc widely disporsed in
the environment. Systematic investigations
of the biological effects of ?C3s have
been undertaken within the pact fow years
to establish tho effects of specific for
mulations on specific species. Studies
have shown that PC3a are an environmental
contaminant. Significant stops have been
taken by D.S. industry to limit further re
leasee of PCbo Uo^thc environment.
?CCa have boon used in throe broad
types of applications as follows:
(1) "Open-ended'' applications? for c::sr.plo, in paints, speciality
inks, paper coatings, plastics, ate.
' '
(2) "Uominally closed" applications; Eor example, as the working fluid in hydraulic &r.d heat transfer sys
tems.
(3) "Closed electrical system* applications, specifically as the insulating fluid in certain kinds of transformers and capa citors.
Effective January 15, 1372, the Monsanto Company, sole domestic producer of PCBo discontinued supplying PCSa to all except manufacturers of electrical transformers and capacitors.
Evaluations of the benefits, risks, and alternatives involved in the continued use of PCBs in closed electrical systems are summar ised in 2.2 through 2.4. 2.2 Benefits. Askaral-filled transformers are used where fire-resistant properties are important. Askarol-filled power and indus trial capacitors are significantly smaller, more reliable, more durable, and safer than oil-filled capacitors. As a result, askarols have supplanted mineral oils in more than 90% of tho power and industrial capacitors mado today. Over the past few decades most of the equipment that incorporates such capacitors has been designed to taka particular advantage of the size, safety, and reliability benefits of askarel capacitors (for example, many types are today lees than 14% of the size of equiv alent oil capacitors and have a life expectancy of 10 to more than 20 years).
Various federal, state, and local codec dictates tho present use of askarel-containing equipment in or adjacent to public, commercial, and industrial buildings, which locations pre sent the greatest potential danger to life and . property.
. NEV 0261ot>
I 739441
WATER PCB-SD0000056928
in the United States, medical re1 changes that would bo required to compensate
coudw since the early 1930**a chow that the
only oevcxxo
x x x o ex x cxporxenGwa by
V.C. workers exposed to nsknrels, either
for the fire resistance of tho askarel-filled units. For certain applications and locations, dry-typo transformers may replace aakaxel-
during tho manufacture'of those liquids or
x*llcd transxormers.
cl electrical equipment coatoinir.g theca
For new installations, although many of
licyaidc, have bean limited to occasional
tho foregoing limitations would still apply,
eases ox aoachroaic chlorecne or other tem
building and installation design provisions
porary skin lesions or irritations.
could bo made to accommodate the use of oil-
,.s.;arol-xiilca transformers .me. CB.pk.cr
filled, open dry-type or sealed dry-type trans
xtorx are oclrvorcd to customers as sealed
formers, provided that necessary technical,
ur.its iron which there is no escape of
code, physical, sire, and cost considerations
asharel under normal operation. Although
aro properly evaluated.
caruain types of equipment failures can re sult m ioes ox some xsxorol to the on--
. Several potential alternative transfimverfluids aro under intensive.investigation .to determine-,
vxror-aeat, transformer* xaxlurcs ..a 1 avaxaed if they will hava satisfactory electrical and
to approximately 0.02t of the units in scr-
operating performance .characteristics. Such
vice per year. With respect to capacitors,
i such losses are limited to approximately
liquids must bo acceptable environmentally, to tho users, and from the fire risk standpoint.
0.0`it ox the units in service per year. , In
addition, limited amounts of ?C3s can get
. Vhp principal alternatives to askarels for
into the environment during the manufacture,
capacitors are cither mineral oil or various
delivery, improper use, maintenance, repair,
types of synthetic fluids. The latter typos
and disposal ox transformers ar.d capacitors.
aro under intensive investigation by the in
Specific control measures have been in
dustry. Mineral oil And theco newer fluids are
stituted by individual manufacturers, and
flammable, fha uso of mineral oil would return
capacitor technology to its pra-1932 level and users ana are xuppxcnontce ane strenghfeued *
by national standards and procedures such as
would necessitate tho redesign and replacement
this standard, which provides information to
of such widely used equipment as flouresccnt
prevent the inadvertent loss of KSs to tho
light fixtures and racks' for power and in
duction-heating capacitors, which could not environment at all stages from initial askarol
manufacture through ultioato disposal.
now accommodate the increased size of oil
2.s PAternator.. For technical and local and
capacitors while maintaining their present
ratings. For the newer types of synthetic national code reasons, it would bo impossible
to rcplaco most askarel-fillod transformers
fluids under investigation it must be determined i
now in service with oil-filled units of
if they will yield satisfactory operating per
formance, are environmentally acceptable and equivalent ratings without major construction
that liquid non-flammability in not required.
739442
NfcV 0 2 6 1 U 7
WATER PCB-SD0000056929
Long boforo thoro uoro any environmental
ctability, chemical stability, and dogroo of
eoncams about PC3n, thoro was a strong eco
flammability (both aro recognized as highly
nomic incontivo to find other loan oxponsivo
resistant to burning. It is for thoso reasons
insulating liquids with tho dooiroblo charac-
that Soction 3 of this standard is intended
toriatica of askarols. Omitting economic con
to apply to capacitor-grado askarol.
siderations thoro ora no technically equiv
3.2 Ceoacltor Grade Askarol. In September.
alent fluids available today.
' 1971, a now grado of capacitor lmprcgnant,
3. CAPACITOR GUIDELINES
Aroclor 101G, was made available to tho in
3.1 C-.-v-rr;-.!. Tho environmental offccts of
duotry. This now grado contains n typical con
uckarols are undor in-dopth ctudy by govern
centration of 0.41 or less by woight of tho
mental and othor agoncioc. Askarols have been hlghor boiling homologuoo of tho chlorinated
considered relatively hornless to humane bacod biphenyls. [ See A5THD3303 -74 (l)1) Aroclor 101G
on safe industrial usago, oinco tho lD30'o,
roplacos Aroclor 1242, which previously was
oxeopt for minor akin and tye irritation.
tho major capacitor impregnant an'd contained .
Thoro havo been, no luiowa instance of human in
around 7t of tho highor-boiling homoloyuos (tho
juries whan they uoro ucod under tho normally
coro persistont in nature). This 0.4% lovoi of
accepted precautions and conditions of handling tho highor-boiling homologuen should bo tho
in both manufacturing and usor applications.
maximum concentration acceptable in any capacitor
Askarols ore being found in tho oavironmont impregnant. Aroclor 1242 and 1254, previously
and in fich and bird lifo. Tho long-term
used ao imprognonts, do not moot this requirement
gonotic and ocological effects aro not yet
and should no longer bo used in capacitors de
completely understood. For thoso reasons, caro signed and manufactured for alternating-current
should bo taken to contain ackarcls and minimlzo applications.
thoir entry into tho environment.
Aroclor 1016 has tho same Underwriters' Labora
Thoro aro tvo general classes of askarols
tories, Inc. flammability rating as Aroclor
used by tho olcctrical induotry. Tho higher
1242.
'
chlorinated grades cro tho more persistent in
Commonly used solvents for clean-up purposes,
nature. Dccauso of thoir higher degree of re includo benzene, kerosene, acetono, trichloroc-
sistance to burning, thay aro used in trans
thano, trichloroethylene, and perchloroethylor.o.
formers whore personnel safety is of paramount Typical vapor pressure data for Aroclor 1016 ares
importance.
Capacitor-grado askarol has a lowor dogroo
of chlorination (composed primarily of tho 3-
chlorino incomers of biphenyl) end a higher de
gree of biodegradability. Generally, it has
0C 25C 150C 200C
" " -
0.001 mmhG 0.006 nsaUG 4.3 rnUIG 29.0' rnmUG
'
At 25C and 760 mmilG prsssuro, saturated air
contains approximately 0.09 mg/1.
not been found in animal lifo. t is used in capacitors, whore tho oxtrosa reelstanco to
NOTEi 1 mg/1 -90.0 ppn (v/v) . 1 ppm (v/v) - 0.011 mg/1
burning roquirod in transformers is of lacs im portance.
1
Numbors in brackets refer ,to corresponding numbers in 7.1, References to the Text.
Although capacitor-and transformer-grade ,
v ' askarols both contain members of tho PCS family,
;
they do differ in conqsoaition, dogroo of bio-
dogradability, persistanca in nature, eloctrical
NEV 026188
-3-
739443 WATER PCB-SD0000056930
3.3 rro?.oY^fi safety and Plant Housekeeping. Tho procedures and Units given in 3.3 axe intended to bo minimum requirements to bo net by manufacturers and usors of capacitors containing askarel. Handling, control, and disposal procoduroo are given, together with exposure limits and indicated antidotes and clean-up procedures. 3.3.1 C-nnnrg.l Safety Precautions. Although it is gonoraiiy accepted that exposure to capacitor-grade askarel is not hazardous provided that simple precautions axo taken, exposure should still be avoided. 3.3.1.1. Vnoors, The odor of askarel is noticoabla well below the maximum air con centrations considered safe. Up to 1.0 milligram per cubic metro of air has been determined to be the maximum safe level of exposure during an 8-hour workday. (See re ference 19) The procedure for performing the necessary analyses.of vapors is referenced in Section B3 of Appendix B. This procedure or its equivalent should be used.
Breathing vapor or fumes from heated askarol should be avoided. Provisions should bo made for adequate ventilation and regula tion of manufacturing operations to avoid open expoouro to askarel (especially at tem
peratures of 5SC or higher). The gases pro
duced when askarel is decomposed by very high temperatures (such as that of an electric arc) in the presence of air or organic in sulating materials contain a very high per centage of hydrogen chloride, and small per centages of carbon dioxide, carbon monoxide, and oxygen. Minute concentrations of this
combination of gases are very unpleasant and
irritating, thus giving ample warning of their
presence. If e>q?osure to high concentrations
of askarel is necessary under emergency con
ditions, an approved gas mask or self-con
tained breathing apparatus should be worn..
Such expoouro should be under the surveillance
of other personnel capable of effecting rescue
in case of an accident. If the odor of askarel
is detected by tho person wearing protective
equipment, he should immediately go into fro.rh
air. All gas masks, respirators, and replace
ment parts should have U.S. Bureau of Minos
approval and be maintained on a regular
schedule in accordance with tho manufacturer's
recommendation.
3.3.1.2 Lleuld. in contrast to the situation
in which mineral insulating oils are handled,
there is virtually no firo hazard in handling
askarol. A limited solvent action (similar to
that for paint thinner) on the fats and oils
of the akin with prolonged contact may lead to
drying and chopping of the skin. A3 with in
sulating oil, some people are allergic to
askarel, and continued exposure may result in
skin irritation. Both the liquid and vapor
are moderately irritating to eye tissue.
Operating procedures should bo such as to
minimize or eliminate contact with asknrolo.
The use.of.porous .gloves that .can absorb.and
retain askarel is to bo avoided. Resistant
2
"
gloves _ should bo used-if contact :is -.unavoidable
Use of_ enclosed .transfer .and .handling ..equipment,
processing equipment, and mechanical washers re
duces direct contact.
2 Tor example, Edmont-Solvit 5-352 (Kersiek of Bridgeport, Bridgeport, Conn), or tho equiva lent.
NEV 026189
7PQ444
WATER PCB-SD0000056931
ikdicir.ol vssho3 or mild detergents fol
pcq section 3.0). Containers used to transport
lowed by the application of cold croon will
askarel should not be used for storago or to
radueo tho irritation resulting from tho con transport othar material without being com
tact of an open cut or abrasion with askarol. pletely cleaned of all traces of askarel.
Safoty glasses with cido shields or a
(Cleaning procedures must taka cognizance of
faco chiold should bo worn whon handling
precautions against excessive exposure and of
askarols. If liquid askarel contacts! tho
the need for proper disposal of contaminated
oyco, tho oyoo thould bo irrigated_irnadiatcly cleansing solvents and materials as cot forth
with largo quantities of running vatar for
in 3.5) Tranefor from chipping containers to
cpproicinatoly 15 minutes and then examined
processing systems should bo through closed
by a physician (A drop of(U.5.P.) castor
piping or tubing with appropriate valves,
oil has been found to reduce irritation).
pumps, otc. provision should be made for
Persons developing a aids irritation or
trapping and disposing of fluid lost by leak-
respiratory tract irritation whilo working
ago or spills froa the transfer system and
with askarols should bo placed under the
froa the storago containers.
supervision of a physician. Ingestion or
Drums to ba retired from use should bo
swallowing of askarols is not generally re
cleaned beforo crushing, delivery to scrap
garded as a problem of tho industry; however, dealers, or othar disposal. Contaminated
snould accidental ingestion occur, a physician cleaning fluids and materials should bo dis
should bo consulted.
posed of as indicated in 3.5.
hands should be cleaned of askarol beforo 3.3.3 Kanufaeturine Iiousekecninn. Manufactur
eating, drinking, smoking, or using toilet
ing equipment and operating procedures should
facilities by moans of waterless hand clean ers3 ar.d v/ipo tov/ols which should then bo
safeguard against loss of askarols to tho en vironment through proper containment and dis
properly disposed of.
posal procedures.
3.3.2 Pulk Fluid 'Shipment?' Receiving- and
3.3.3.1 Processing Area Control. Enclosed sys
transfer. Shipmont of askarol from point of
tems of sealed piping, properly gasketed joints,
manufacturing to point of rccoiving should
valves, containers, and processing chambers
be done in closed containers such as rail
should bo used for all operations where askarel
"tank cars, truck tanks, marino or bargo tanks, temperatures nay exceed 55C. Enclosure chould
or coaled drums. In caso of an askarol spill preferably extend to all other portions of tho
during bulk fluid shipment, roforcnco should
system insofar as practicable.
bo mado to paragraph 6.0 which provides pro-
Establish containment methods and/or pro
codurco. for control and listed authorities to cedures for all askarel processing areas to
bo notified. Containers should bo labeled
prevent loss to sewer systems by spillage,
as to contents and carry a label cautioning
leakage or other uncontrolled conditions or
against loss of fluid to the1 open environment events.
3For example, Pow'r Klecn Kandcleaner, (Koodbino
Chemical* and Resoarch, Inc., Medina, Ohio or Man's hands, Oak Industries, Inc., Eoosick Falls, Maw Fork)
,,
.
'
NEV 046190
739445 WATER PCB-SD0000056932
1.2.2.2
;.r.c. Control of. Llouid Askarel
should be collected within the containment area
Wastes. Askarel-containing liquid wastes nay
for properly controlled laundering.
occur in manufacturing from sources such as
3.4 Control of Plant Effluents.
the following: 1) Liquid aokarel contam-
' 3.4.1 Water Effluents. The industry goal is to
inatod during processing which is unsuitable
eliminate askarel in plant water effluent streams.
for reclaiming as a dielectric fluid,
However, it is recognized that existing drain sys
2) liquid aokarel from oolvont operations or
tems in capacitor manufacturing plants are prob
water and detergent type washers, 3) vacuum .
ably contaminated as a.result of past practices,
pump oils contaminated with askarel, 4) steam
and askarel traces may continue to decrease with
jot vacuum system condensates contaminated
the proper containment of askarel wastes and no
with aokarels, and S) askarel containing
further discharges into drain systems. Other
materials from laboratory samples.
sections of this standard provide that no aeknrcl
Waste fluids containing askarel should bo
wastes of any kind be disposed of in any water
collected (by means of traps, drip pan3, trays,
effluent streams and that accidental rpills
etc) and disposal should be in accordance with
be prevented from getting into such streams.
3.5.
3.4.1.2 Concentration Limits. The ERA has pro
Spills of askarol3 should bo contained and
posed water quality criteria to maintain FCE
cleaned up promptly by moans of absorptive
concentration in rivers and Hakes below detec
material, such as sawdust, or trapped and re
tion level. Requirements under Sections 307(a),
moved by pumping or other suitable means.
307(b) and 311 of the 1972 Amendments *to the
Disposal should be per 3.5.
Federal Water Pollution Control Act are under
3.3.3.3 Tyoos and Control of Other Askarel Con review (197C-77) and the latest revisions will
taining wastes. Saturation of materials with
apply. State and municipal requirements must
askarels may occur in manufacturing from the
also be met.
following sources: 1) Saturated earth or other
Further information may be obtained from an
absorbent media from filtering operations or
Environmental Protection Agency Regional Offico.
from cleaning up spills, 2) saturated filters
A listing of these offices is contained in
from vapor control devices and other filters, . Appendix D.
3) saturated wastes such as paper, rags, etc.
3.4.1.3 Monitoring Streams. On a regular basis
4) saturated spent gasket materials and 5) capac consistent with plant situations, all effluent
itors failing tests or otherwise designated for streams should be analysed. The procedure for
disposal.
* All of the above items should be collected
performing the necessary analyses is per ASTM Method 03304. This procedure or its equivalent
for proper disposal. Wiper rags, protective 4
clothing and other extraneous materials which
should be used.
axe likely to be eoilod should preferably bo
made of disposable materials. Other materials
4'
For exanplo, Edmont-Wilsnn, 1294 Walnut St., Coshocton, Ohio 43012, ow Slosman Corp., P.O. Box 3014, Asheville, W.C. 28802
NEW 0261^1
739446
WATER PCB-SD0000056933
3 . 4. 1.4 .`'.thodf) for Minj-mis/.nn Jiff ie.oht Sfero.-in 5isp6cai should bo Coho, in a. manner which in
Co-Mamina, tion. Tho ideal approach is to isolate consistent with proper concern for tho environ
totally all effluents that could be contanina- ment end minimizes any release of askarols to
ted with ar.karcls during manufacturing processes tho environment.
and prevent them from being discharged from the 3.5.1 Disposal of Capacitor Units. Scrap ca
plant. Carbon absorption,limestone beds,and sol pacitor units can be generated during manufactur
vent extraction`are techniques.that could be ap ing' processes or during field service. Produc
plied to reduce the askarol content of effluent, tion rejects are those capacitors that nrr. re
streams, These techniques may bo moot useful in cleaning up water used in plant*processing and to permit recycling. 3.4.2 .Mr n.ffluents. The industry goal is to
jected' after tho impregnation process in the course of production by the capacitor manufactur er. They cry bo. rejected for mechanical or
eliminate aokarol vapors in plant air effluents, electrical reasons.
riant operations involving askarels at elevated
Field rejects are those units that arc re
temperatures in excess of 55C should be per
jected or, for other reasons, are to be scrapped
form,ed, wherever possible, within closed sys
aftor shipment from the plant where they were
tems. Filtration of plant air effluents, to
manufactured.
mininiso PCDs entry into the environment,
Capacitor units should bo disposed of intact,
should bo accomplished whoro onvolvcmant of
or if locking, in scaled drv.-nn. Tho small amount
air borne PCDs may occur from open operations., of liquid to bo drained, the integrity of intact
3.4.2.1 Monitoring. All plant air effluents should bo sampled and analyzed on a routine
units and the necessity for eorplc:: control over drainage procedures makes intact disposal prefer
basis consistent with plant situations. Tho
able.
procedure for performing tho analysis i3 per
3.5.1.1 Production P.ejcets. F.cjcctcd capacitors
ASTM Method D3304 (See Appendix B3).
. in capacitor manufacturing plants represent a
3.5 Scrao-Dirnonal Procedures. The m&nufac-
concentration of askarol. it is, therefore, im
turo and uso of capacitors involves processes portant that disposition ha made in a manner con
which produce askarcl-saturatod solids and
sistent v?ith proper concern for the environment.
liquids containing or composed entirely of
Preference should be given to disposal of capac
askarol, which should be disposed of as wastes. itors in cites approved for hazardous wasto dis
Specific sources of these materials ere de
scribed throughout this standard. They may
bo placed into three categories 1
1) .Capacitor units impregnated with
askarol, production and field re jects
, .
posal (See Appendix A).- Another alternative,but less desirable, would be disposal in approved landfill cites. Caro should bo exorcised to insure that no loss of liquid will occur during transportation
2) Manufacturing process liquid wastes containing askarol
3) Solid wasto purposely or accidentally saturated with askarol
to tho disposal site.
.
,,
Incineration of scrap capacitors in facili
ties designed to accept such'solids would pro '
vide a preferential alternative to approved land
fill sites when such services become available.
NEV 026192
739447
WATER PCB-SD0000056934
2.3.1.2
r
KhcrOVCX practical, til prafcrablo aispoonl procedure iu an approved
ackorol containing capacitors should ba re
landfill uite. Sea Appendix A for listing of
moved prior to disposal Oi! equipment. This
Facilitioo.
'
precaution will u'iwico onviroiuunnial control
3.5.4 Packaging and Shipment.
procedures and insura that by removing those
3.5.4.1 Transportation to tho disposal facility
capacitors thoy do not ultimotoly dicporco
chould bo in containers that will prevent leak
their aakoroi contents into an unapproved
_
landfill site.
age and accidental loss of askarsl to the n-
i
j vironmont.
Af tor removal from equipment, capacitors ] 3.5.4.2 Containers should be labeled as to con I
should be daspaact* in accordance wrth tho proTM tents and precautions relative to loss to the
ccduros for production rojccts (3.S.1.1).
1 environment par 3.3.2. i
Where removal of aoharoi-containir.c; capacitor^ 3.5.4.3 Containers for this purpose cannot be
iron equipment is not practical, that equip- , used for any other materials or they should be
meat should ba disposed of only in approved rotirod frou'service until they are completely
landfill sites.
cleaned. Any solvents used in cleaning these
s.i.2 iii'-.rv1,-) r.<? ?,<c-aid Waste;.:. All wasto
containers will bo contaminated with askaral
asharol or liquid wastes containing aokarcl
and chould bo disposed of according to the same
should ho disposed of in accordance with ono ; procedures described in 3.5.2.
of thw procedures given in 3.5.2.1 or
3.5 Lr.'ocllnr'. Capacitor units vary greatly in
3.a.2.2. However, proforonco should bo given
sire and in end use or application. Small capac
incineration, 3.3.2.1.
itor units are frequently applied as a component
5.5.2.1 Incineration. Proper incineration
of another pioco of equipment, such as a fluores
i.ust involve a suitable balance between dwell
cent lighting ballast,a roadway of area lighting
tima and tcaipcraturo in tho incinerator plus
luminairo, a motor, etc. In such applications a
oxygen availability, and finally, cuitablo
label on tha capacitor unit referencing approved
scrubbors to remove tha KCL that will bo
disposal procedure would not normally be visible
for/uid; for example, 2-soconc dwell timo at
when tha pioca of equipment is disposed of.
2000F and 3t oxcooo oxygon in stack gas, or
For tho foregoing reasons tho methods of label
1.5 second dwell tima at 27CQF and 2t oxcqsg
ing for email capacitors and large capacitors are
oxygon in stack gas. Vhoao facilitioo should meet tha cppli-
cabla state requiromaato and should control effluents within tho limits cot forth in
treated separately in 3.6.1 end 3.6.2, respectively 3.6.1 Small Units. Small capacitors are defined as thooo that contain askarel in quantities up to about 2 pounds each and in which the free liquid
>O-!'
<3
O
this standard. ' 3.5.2.2 Chemical facto Disposal. Macro incinoration ic not feasible, sites which hava
\ dooc not oxcocd 0.4 pounds. They are hermetically j coaled in mctnlic casoo. it is recommended that
shipping containers from'capaoitor manufacturers
i>U Z.
been classified by atato ogencioa as suitable
should bo labeled as to contents and that trans
for disposal of chouicul vasto liquids should bo used (Sao Appondix A).
3.5.3 Disposal of Solid VTr.stos (Soo 3.5.1 for scrap capacitors), All colid vaatoo which havo boon saturated with askarol should bo plaood in leak proof containers and preferably trans ported for disposal by ineinoration. A loco
porters bo given instructions, in accordance with paragraph 6.12 as to procedures in the event of a spill.
Zf, howovor, a label of tho capacitor is required by statuto or by spocifio manufacturers, the follow ing is suggested!
Contains PCas. Use care in disposal.
' 739448
WATER PCB-SD0000056935
'The shipping container1 label, yellow on
or spillage that may have occurred in shipping.
clack, ikould contain the following information: If leakage is evident, tho causo should be
C.YdVIcn" Contains PC33 (Polychlorinated
Liohanvis) that are envirort'Acn-
tal contaminants. In ease or
leaks or soills. restrain dic-
charca and consult manufactus-ar.
In tranoDortation emergencies,
call National Kesponco Center
(GOO--'.24-CC02) and Chcmitrec
(200~!2'i"5|300) o Avoid pro
longed-breathing or vapora or
'
mists, contact with eyas or
.
skin. Disposal ohould bo in
accordance with ."ITS! C-107
.......... Cuiuelineu or applicable
L't-'iiO wacI I?"Cs*ClT>-- Liwilfciil'CCU * *
corrected and tho spillago soaked up with ab sorbent materials such as sawdust, followed by a cleanup of tho affected area with kerosene or other approved colvent such as perchloroothylono. All materials used should bo collect , ed for proper disposition an described in 3.5. 3.7.3 Installation and Periodic Inspection. Large capacitorc should bo installed in new
Small unit capacitorc aro applied ao a
facilitioc such that if a leak should develop,
component of a largo piece of equipment,
askarolo can bo restrained from reaching the
kanufaciurcrs utilising askarel-filled capac
environment. Depending upon tho typo of in
itors should affix a label referencing this
stallation, consideration may bo given to pans,
standard or describing disposal procedures
dams, traps, standpipes, dry wells, absorbing
consistent with it.
agents, otc.
3.G.2 T.-rr-n Unite. Largo capacitor units aro
following installation, the unit should
defined as thooo which contain more than 2
again be inspected for any damago or leakage.
pounds of askarol. Tho manufacturer ohould
It is recommended that periodic in-service in-
affix a label in a cor.spicouo place on the
epectior.c be made for leaks.
capacitor, referencing this standard or des
cribing disposal procedures consistent with it.
As a minimum, tho labal ohould contain inform-
-..-.ation listed in 3.G.I. 3.7 Infow-tlon for Uoc?:n of Larne Capacitors
5.7.1 cenr-ra?.. Large Askarol-fillod capacitors
contain more than 2 pounds of askarol and de
livered to customers ao sealed units from which
there is no escape of askarol under normal
operation. Although certain types of equip
ment failures can porrnit loss of soma askarol
to the environment, such cases aro extremely
rare.
'
3.7.2 Transportation and P.eceivinc. Immediately
upon receipt of a shipment and following any
transportation or handling accident that could
effect the integrity of the capacitor enclo
sure, the transportation vehicle, enclosure,
and fittings should bo examined for any leakage
4. Transformer Guldllnes.
4.1 Central.
.
4.1.1 Askarols of various compositional types
aro currently in use (for the general proper
ties and typos, see ASTM D2283-73a(20)) . The
trademark designations used by manufacturers for
liquids containing PCBs aro given in Appendix
C.
Under arcing conditions, the gases produced,
though predominantly 1 consisting of noncombust
ible hydrogen chloride, can contain varying
amounts of combustible gases depending upon the
askarol typo.
4.1.2 Safety Precautions. Based on about 40
year3 of safe industrial usage, askarels have
been considered as relatively harmless mater
ials to humans There has been no known instance
of human injury when askarels are used under
tho normally prescribed conditions of pre
caution and hanc'linc.
'
NEV 026194
'
TOOM aci WATER PCB-SD0000056936
iiL 1-.V C**U'u<
W*A VO*/Gj wO
io laG'C i"*aEaiTC*GU pTG"
Viuuu
jGt'J,Lc piTL.CC*'U'ulCrfcli OiTC ua*tC'A, OiC*"
x.. e--u or uccxdont. Xs. uilVJ OUOiT Ol
askarel or its arced products is detected by t'no person wearing protective equipment,
^0JU*'C JuiUxti'
j>l bO uVOll^wu G'J tii^u^^u^IbCQa
ho should immediately go into fresh air. All
4i X 2 * 1 V * ~~.`", . TAO 0u07 0<hi GGkGjTGl i
gas masks, respirators, and replacement parts
rt^wiccwblc well bciow tao rrGXi-*iYwi\ ww*o axor
snould havo U.S. Bureau of Kinoo approval
COltCCaViX* u wXGAG wC'pCriC*i*i^ VipO'i* biTG CGiiYpOG jL*"
and bo maintained on a regular schedule in
tiOTi OX. ;GGC i*GiCGlTOl. GGCG f 1TOm* CjbS* tG 1. * 0
M) X Jk
W%> ^JvY C Ml) XG (tt2 bM Cl G*.
liutl
,
accordance with the manufacturer's recommen
dation.
'
tie iciaxxaccL bo bo bho uppeiT cg.yu level o*r
4.1.2.2 Liruifi. In contrast to the situa
ci> 30uU-.*U UUi'
Qii y*"hOUdT WOCiCiuy (jCvj i0"
tion in which mineral insulating oils are han
X' C I'C G G' c (*y))
dled, there is no fire hazard in handling
VGG ^X'0C`CGUX*G X'OIT pCiTXOXGaXng bj*Q 7>GCuu"*
askarels. A limited solvent action (similar
anaiyaia is contained in ASTM Method
to that for paint thinner) on the fats and
yGCG .*ppCi*uiM *i/
oils of tno skin with prolonged contact may
2/X*vj*-bax*g vepoiT Gi* iitinco xi.*ci* Gxggcg
lead to drying and chapping of the skin. Aa
uwkl*v-iJ JuOmIu GO XVwXtiCtl b liiQ'A CGiYCcn**
with insulating oil, soma pcoplo are allergic
'Ci-'MuiUi'i^ Oil Vu^O^J Cuil CuUuO i..YIumw^Cu G'j-
to askarel, and continued exposure may result
thu cyu.mj f ViOuC/ tbiTGiu'u , *r*G uppes* x'GL/yxxra*"
tox**' 'd'uCu. w'x'ovisu.one ^nnl-. ho xgggu xgit
in skin irritation. Both the liquid and vapor are moderately irritating to eye tissue.
wuc:aug*cg ventilation to avoid open oxpoouro
Operating procedures should require avoid
ox not c.vt'Cairdw (5b C ox" bigbo^r) V+tO gases
ance of contact with any askarels. The uso of
'ofGaucwiu \/tuu uOrva>cd as GtcQi\)po*rfCa by vc*.y
porous glovos that can absorb and retain
hi^'h 'tL-4-tPvj.M-*tt!c ex (sugg as tnat oa an dele* trie are) in tho presence of air or organic insulating Materials contain a high pcrccntgw of hydrogen chloride which is highly tonic, and s.tall percentages of other gases*
askarels is to bo avoided. Resistant gloves and aprons such as the polyethylene or fluoro elastomer type should be used if contact is unavoidable. For some operations, it has been found advantageous to uso non-porous, dis
hi.nutc concentrations of this coiabination of posable aprons and gloves. In case of spill-
gates are very unpleasant ane am/ca'cing, u*<us giving aiup^-o v/urmng or LitO^r p*.luci*cu
exposure to l*ixgh concentrations or nsxnrcl' or its creed product- is r.ocoosary under em ergency conditions, an approved gas mask of the organic canister typo, or self-contained breathing apparatus, must bo worn. Such ex posure 'should be under the surveillance of other personnel capable of effecting rescue
ago on clothing, the clothing should bo re moved as soon as practical, the skin cleaned with waterless cleaners or solvents such as kerosene, and wiped dry with disposable towels. These towels should bo disposed of as PCB con taminated solid wastos. See Section 4.1.6.2.2. Clothing and shoes saturated with askarel should be discarded (burnable waste). Con taminated clothing may be reused providing that
*?or example "VxTON
NEV 02619b
739450 WATER PCB-SD0000056937
....'.I, morGegnxy clo^no^ usxng segue-- gucee soxvonts or a sogrogatoo dogreusor,
2 .Vyi-II Procedures - Bulk liquid shipment;.. Soo Section 6.
thun to*xO\/od by normal xaundoring. (xaunc*cr-- 4.1.4 RacclvincT, Handling, and Storage of
irg alone is not sufficient.)
Askc.rclii.
Medicinal washes or mild detergents
Askurels are shipped in tank cars, tank
followed by the application of cold cream '
trucks, steol drums, metal cans, and taau-
wall reduce *ano xrrxtatxoa rosuxtmg rrem
sumpia containers. When received, all con
tho contact of an open cut or abrasion with
tainers should be inspected for leaks.
as /Carul
4.1.4.1 StorccG Tanks. Storage tanks should
Safety glasses with side shields or a
bo oractcd so that inspection can be made for
face shield should bo worn when handling
leaks or spills. Construction should be such
as,carols, byos that hovo boon crposca to
that inadvertent leakage or spills are pre
laquad as^arox snouxe. no xxrxgatcc. xnmcc.1-- *'
vented from reaching streams and sanitary or
atcly with largo quantities of running water
storm sewers.
ror approkrmatOxy x2 minutes ana tnen exam
4.1.4.2 Tank Cars and Tank Trucks. All bulk
inea oy a pny-icxan. (.* atop or (vJ.S?/cas
shipment cquipmor.t should be inspected for
tor oar i.kiii' tucs founa to roaueo irritation.) loaks immediately upon receipt. Drain pans
Ingwbion or swallowing of askarcls is
should bo provided to prevent spillage from un
not general*'/ rcgaraca as a pxOnlOa. or tno
loading hosoo and connections. Askarol liquid
ir.duatry;- however, should accidental ingos-- collected in drain pans should be placed in
tr on occur, a pnys*cxan snouxd bo co..sul tea *
drums labeled "Scrap Askarel* for disposition
bands should bo cleaned as noted above
in accordance with 4.1.5.2.1.
before eating/ drinking/ smoking or using
4.1.4.2 Stool Drums, Cans, and Test Samnlc Ccn-
toilet facilities.
tr.incrs. On delivery, all such shipments should
bo carefully inspected for leaks. The contain
4.1.2 birr.id Transport Containers.
ers should be stored indoors in an area espe
4.1,2.1 Tr.-r.snort Container Mnrkinc;. Any con cially selected for this purpose. A curb
tainer, such as tank cars, tank trucks, drums, should enclose the area to provide a basin for
cans, etc., used to transport transformer
containing tho askarol from one or more con
askarals, new or uuad, should bo labeled
tainers should tho containers be damaged. The
with tho following (yollow on black):
v'
"CAUTION" Contains PCDs (Polychlorinated * Diphenyls) that aro environmental contaminants. In case of leaks or spills, restrain discharge and consult manufacturer. In transpor tation emergencies, call National
Nasponso Center (000-424-8802) and
Chcmtrcc (300-424-9300). Avoid pro
longed breathing of vapors or
mists, contact with eyes or skin.
Disposal should bo in accordance
with ANSI C-107 Guidelines or
applicable state End Federal sta
tutes."
'
area should not have a drain that is connected to a sanitary or storm sewer. .
If an indoor storage area is not possible, the containers should be stored under a leanto with similar containment capabilities.
NEV 0261V 6
739451 WATER PCB-SD0000056938
.'.1.5 Control o:r Water Effluents. The Indus- ` try goal is to eliminate askarel in water effluent streams. However, it is recognized that existing drain systems from manufactur ing plants, repair shops, and installation sitos may be contaminated as a result of past practices. Other sections of this st/indard provide that no askarel wastes of any kind be disposed of in any water effluent streams and that accidental spills be prevented from getting into such streams. 4.1.5.1 Concentration limits. The EPA has proposed water quality criteria to maintain rCD concentration in rivers and lakes below detection level. Requirements under Sections 307(a), 307(b), and 311 of the 1972 Amend ments to the Federal Water Pollution Control Act are under review (1976-77) and the latest revisions will apply. State and municipal requirements must also bo met.
Further information may be obtained from the Environmental Protection Agency Regional Office. A listing of these offices is con tained in Appendix D. 4.1.5.2 MonitorInc Streams. All plant effluent streams should be monitored on a regular basis. The procedure for performing the necessary analysis is contained in ASTM Method D3301 (See Appendix B). 4.1.5.3 Methods for Minimizing Effluent Stream Contamination. The ideal approach is to totally isolate all effluents -that could be contaminated with askarels during manufac turing processes and prevent them from being discharged from the plant.
4.1.6 Flroor.nl procedures and Servicer-.
4.1.6.1 Sources of Material;*. R^ouirinc Soocinl
Hardliner an0. Dlroo.ral Procedures, liquids con
taining PC3o and solids containing or con
taminated with PC3s may come from many
sources including transport containers, trans
former manufacturing processes, in-test failures,
liquids contaminated beyond reclamation, in-
scrvico transformer leaks and failures, aokaxel-
fillcd transformers scrapped for any reason,
sample containers end handling equipment.
'
4.1.6.2 Classlficntlon for Disaor.nl of Mater
ials Containing PCBs. In general, there are
four types of materials requiring disposal:
burnable liquids contaminated with PC3s; nor.-
burnable liquids contaminated with ?C3s; burn
able solids contaminated with PCSs; and nen-
burnablc.solids contaminated with PC3o.
4.1.6.2.1 Burnable: LiQuids. Liquids containing
PCCs . requiring disposal by high-temperature
incineration may consist of the following:
(1) PC3s contaminated with mineral oil.
(2) Mineral oil contaminated with PCSs.
(3) Monrcclaimable contaminated trans
former askarels, arced askarels,
askarel3 from manufacturing spills,
sump accumulation, askarels from
holding basins, drip and drain pans,
washings, sample jars and containers,
' etc.
4.1.6.2.2 Honburnablo Llcv.lda (Water) Con
taminated with PC3n. Water contaminated with
PC3s * may be treated by such means an activated
carbon filtration or by. a reductive dechlorina
tion process, providing that the effluent meets
Federal and State water effluent standards.
Such liquids may also be disposed of, packed in
suitable containers, in approved landfills. See
Appendix A.
.
NEV 02619 7
739452 WATER PCB-SD0000056939
4.1. C. 2. 3 ' ".bio Sol.id VTunto M;:/co:r?.r Is
Cc.. I'.'." ' \ ''h
TnosG mu'ccrm^c cxi*
L-c diopooc-d of by high-tcmpcrature incineration
and conoiot of collulocic materials, rags,
prcssbooru, v/oou Suwuuutf fulxcr's eurm m
bulk ox in cloth bugs, blotter papers, nitrilo
or cork gaskets, etc.
4.1. C. 2.4 rr',-'`-"V7i-.>?' Solid U-r.te Totrrlnls
Co:; ..i".OT nor.t.~r.r'.:-..~tr.c! with ?cr,r.. Theco
may coaurst of acoolf coopGx,
a1'Xuxiva., ralter units or the shoox. moon conTM
struccion type*, us/curex arums, cans, otc.
MufwX-iais of this nature should bo allowTM
aa to tram wxuh Ixquxas colxccuoa x*. drxp
^ui'.u, etc. Further removal of adhering PCAs
^.*ouwd Oa ucc'empxisnod oy vapor ocgxeasing,
v;__,t3ng or solvent extraction wxth kerosene
or other approved washing liquids ouch ao
oe'rov.xoroutnyeono. Accumuxa'cca xrqerds
saouxu oo axsposcG or ao inuxeated m
4.1. G.2.I. Solid r.atorialo as cleaned above
iuay bo nun*xlca ao sorrel scrap.
Corl structures may oq dismantles wrth
burnable Material removed. Metals should bo
treated as noted above > ana burnable solids
disposed of in accordance with Section 4.1.6.
2.3. hr. alternative but loss desirable pro
cedure for disposal of coils, cores, burnable
,;astu, etc., is to suitably package ar.d bury
in an approved landfill cite. Seo Appendix A.
4.1.C.3 Shi-r.'.nr.t of Fere."? T.icuifls For ftis-
All licyuia scrap Material should bo
placed in appropriate motal transport con
tainers, properly labeled (Section 4.1.3.1)
for shipment to a company offering an accept
able disposal service (Appendix A).
'
4.1.5.4 Shipment of Burnable Solid Waste Material Containing PCDs for Disposal.
Material of this type should be placed in a
liquid-tight container meeting Federal and State transportation requirements, and
acceptable to the disposal organization. lae
container should bo properly labeled (Section
4.1.3.1) for shipment.to a company offering
an acceptable disposal service (Appendix A). 4.1.G.5 Liquid and Solid Waste Disposal Ser vice Organizations. These facilities should
moGt the applicable requirements of the state in which they are located and should control
effluents within the limits referred to in Section 4.1.5.1. 4.2 Guidelines for original Manufacture, Ser
vice and Repair Shops.
4.2.1 Plant Housekeeping It is necessary to
assume that in filling equipment with askarel,
and during further handling of this equipment,
an askarel spill may occur. Therefore, it is r.coscary to provide facilities and a procedure
for cleanup to prevent contamination. 4.2.1.1 Askarel Filling Area.
4.2.1.1.1 It is desirable that the askarel
filling area be adjacent to the test area and
final shipping area to minimize the danger of
damago to units during handling. 4.2.1.1.2 The main manufacturing area for
filling equipment with askarel should be pro vided with impervious surface floors or suit
able basins so constructed that any inadvertent
leakage or spills are prevented from reaching
streams, sanitary sewers, or storm sewers.
All askarel-handling equipment, such as pumps, hoses, eto., shall be of the askarel-resistent
typo.
.
NEV 026198
739453 WATER PCB-SD0000056940
Drip pins shall be provided for
for disposition. Cloth bnd filled with fuller'r:
hose connections and filling valves.
< .2.1.2 Special Containers for Sera'? Mater-
i !\ 1 s.
.
earth should be placed in the "serve? dvreaeie ASKAREL VIASTE" container for disposition. 4.2.1.4 Tonrd.own of Units for Repair or Reran.
4.2.1.2.1 Drums labeled "SCRAP ASKAREL" should bo available for handling all spilled and waste Askarel from sumps, failed units,
4.2.1.4.1 Drain all askarel from tho unit either into a holding tank for reuse or into tho drum labeled "SCRAP ASKAREL" for disposition, allow
drip pans, sample jars, etc.
'
4.2.1.2.2 Open-head drums with suitable
closures and labeled "SCRAP DORNASLE ASKAREL
ing sufficient time for all of the askarel to drain from the coro and coils. 4.2.1.4.2 Ecmovo tho core and coil assembly
VASTS" should be available for handling con taminated colluloso insulation, rags, papor,
from the transformer tank and place over a suit able drip pan.
precsboard, wood,gaskets, sawdust, etc.
4.2.1.4.3 Place all materials in tho appropriate
4.2.1.2.3 Separate containers for handling steel, copper, and aluminum, each adequately
salvage containers during dismantling for later
disposition.
.
marked, shall be provided for the compononto 4.2.1.4.4 All used materialsincluding rags,
of contaminated coro and coil assemblies.
sawdust, tape, etc., regardless of quantity,
Those containers are required for the various shall be put into tho appropriate containers for
materials when repairing or scrapping
disposition.
assemblies. 4.2.1.2.4 Containers for supplio3 of mater
4.2.2 Trans former Labeling and S'">ir>ment V
4.2.2.1 New and. Rebuilt Trarrformers. All new
ials for absorbing small askardl spills or
and rebuilt transformers that contain P.CSs shall
cleanup of larger spills should bo provided. havo a label of adequate durability, permanently
4.2.1.3 Conditioning of Askarols.
and prominently attached to tho tank by tho manu
4.2.1.3.1 Askarel Conditioning Eruiomont.
facturer, giving adequate warning and instruc
The conditioning unit should be located
tions . A suggested label, yellow on black, in
oibher in tho storage tank area or in the . cludes the following:
main transformer manufacturing area for ' filling'with aokarol.
4.2.1.3.2 Fuller*s Earth. Conditioning of now askarol or recycled askarcl requires fuller's earth treatment. The spent fuller's earth in cartridges or bags, when replaced, should be allowed to drain thoroughly over drip pans to remove as much liquid askarel
"CADTION" Contains PCEs (Polychlorinated Diphenyls) that arc environmon-
. tal contaminants. In case of leaks or spills, restrain dis charge and consult manufacturer. In transportation emergencies,
call National Response Center (OOC-424-CCC2) and. Chemtrcc (COO-424-D3CO). Avoid, prolonged breathing of vapors or mists, contact with eyes or n'cin. Dis posal should be in accordance ` ' with ANSI C-107 Guidelines or
, applicable state and Federal eta
, ' ` tutes."
as possible. The cartridge units of steel
4.2.2.2 In-Service Transformers. The Transformer
mesh construction should be placed in the'
manufacturer should make available suitable labels
"STEEL CONTAMINATED VIIT3 ASKAREL" container with similar warning as shown in 4.2.2.1 for use
on eristing transformers.
'
4.2.2.3 Shipping papers should contain the warning
NfcV 0 2 6 1 9 9
7PQ4M WATER PCB-SD0000056941
4.2.3 T.'i ~cxr .tlon for Transformer Users
4.2.3.1
ml. Aukarol-fiiled transformers
are delivered to customers os coaled units
from which there Is no escapo of askarol
under normal operation. Although certain
types of equipment failures can permit loss
of soso askarol to the environment, such,
case.* are oxuremoly rare.
4.2. 3. 2 ?::: ..--xrtr.tion r.r.d Receiving. im- .
mediately upon receipt of the equipment and
following any transportation or handling
accident that could affect the integrity of
tito f.n*K, x*usnxng*s, or ruax--tors, tne trans--
portataon vc..xcxo, tunm, ana rxttxngs should
oe cramxncd tor any Icarago or cpxllago tnat
;,,ay have occurred in shipping, If leakage is
evidentp tho cause should ho corrected ana
t/.e spillage seamed up warn aosoment mater
ials such as sawdust, followed by a cleanup
of the affacted area with rags soaked with
kerosene or othor approved solvent such as
perchlorocthyleno. All materials used should
be collected for proper disposition as cos-
cribea xn 4.1.5.
4.2.1.1 ".v'.t.-.llntlon end Periodic Inspection.
Transformers should bo installed so that if
a leak should develop, askarols can be re
strained frost reaching tho environment. De
pending upon tho type of.installation, con-
slaoration may to gxvon to pans, dams, traps,
standpipes, dry wells, absorbing agents, etc.
'following installation, the unit should
again be inspected for any aamago or leakage.
It is recommended that periodic in-service in
spections be made for any leaks.
4.2.3.4 Filling, filtering, or Drying hskcrcl.
Xost askarol units are shipped with the proper
amount of ashore!, but if it becomes necessary
to topv off a unit, the manufacturers1s in
structions should bo followed.
If it is necessary to dry an aokarel unit
or to treat an askarol unit with fuller's
oarth, instructions should be followed. When
filtering or conditioning askarol, all of the
precautions previously described for drip pans,
prppor disposal of filter media, etc. apply.
<.2.3.5 Sampling. It is common practice to
sample askarol from a transformer for periodic
maintenance testing. As previously described,
such samples should be taken in a manner to
avoid any contamination of tho environment.
Washings should be collected for proper dis
posal. Field and laboratory test samplos,
washings, etc., should also be collected for
proper disposal.(See Section 5).
4.2.3.6 Transformers 'Installed in Moving
Vehicles. In the event of a leak or accidental
spill, tlie procedures outlined in Section 6
should be followed.
.
4.3 Ro.trofilling Apparatus Containing Ar.karcls.
It is not recommended that apparatus containing
PCS liquids be changed to other liquids. It is
recognized that the best possible change-out
procedures will still leave appreciable PCEa
in the apparatus. Apparatus that has contained
PCBs which has boen replaced with another
fluid should be labeled as indicated below, and
the disposal ultimately should follow the same
disposal procedures as those recommended for
PC3 liquids and PCB-filled apparatus.
NEV 076400
739455 WATER PCB-SD0000056942
Libel (yellow or. black)
6 Soil! Notification ana Control Plan
CAUTION: Contains liquid con taminated with PC3s an cnvirorm.cntal con taminant. Changed to (describe liquid) on (give date).
4 . v Dis-.orul.
Tho ultimate disposal of a ?CS-cor.tuir.t-
iag ti.-anoior.uor may bo accomplished by tho
following procedures?
1. Contract with a qualified organisa tion for disposal of the complete
U>* ib OiTluCiT *
2. Where acceptable facilities aro available, tho following alterna tive procedures aru rucorriondod:
(a) Always drain tho liquid and '' dispose of it by approved
te**GoT XOti *
(b) 'for tho solid components or for the entire structure, either of the following procedures aro *wCClu>bCiiUCd
Polychlorinated Biphenyl(PCDs)
Tne immediate actions needed are to contain or restrain liquid spills with tho boot moans available and to notify "C2ISMTRSC" and "The National ACoponsG Center."
"The basis for this spill notifica tion and control plan relies on Chomhroc to advise on the immediate actions needed to contain or restrain the liquid spill with the best moans availablo based or. listed instructions. Tho National Response Center will notify all interested parties, i.e. Federal end State authorities and the manufacturers involved, as well as give guidance on action to be taken."
FAILURE TO REPORT SPILLS TO PROPER AUTHORITIES KA RESULT IN CRIMINAL PENALTIES.
C.l Chcmtrcc
6.1.1 What is it. - Chemtrec stands for
Chemical Transportation Emergency Center, a
public service of the Manufacturing Chemists
i. Dismantle, wash and dispose
in accordance with Section
4.1.6.
'
Association at its offices in Washington, D.C. Chemtrec provides immediate advice for
ii. Ship entire solid struc
ture to acceptable organ isation for disposal.
thoso at the scene of emergencies, then prompt' ly contacts the shipper of the chemicals in
iii. Chio to acceptable land-
fill disposal .sita. (See
f,ppu.or^ A).
1 volved for more dotailad assistance and appro priate follow-up.
3. Pi morel of Laboratory Samples Contair.-
Chemtrec operates around the clock - 24 hours a day, Geven daya a week - to receive
The disposal of laboratory samples and materials used for testing and experimental purposes which contain, aro impregnated with, os* contaminated by ?cs (askarcls) must be carefully controlled. Thoir disposition ' should bo made in a manner consistent with procedures in 3.a.a and a. 53 (Capacitors)
direct-dial toll-free calls from any point in tho continental United States through a wide area telephone service (WATS) number,
800-424-9300 (483-7616 for calls originating within tho District of Columbia) 202-483-7616
for calls originating outside the continental U.S.).
ana ui.d (Transformers).
NEV 026201
739456 WATER PCB-SD0000056943
6.1.1 It i* ree'o..neh--uu t.-- w a*x p**.,t a..a
u.<.
'i.U .u i-lcnrr/.ucwt
p.'w^ent tiiui'iU.uCuurersof PCbii and Pwu--co.i--
I'c is rbco.wieneed that all users should have an
twining - equipment bo listed with Cncmtruc
or.-sita spill prevention countor-moaEure and
Contact MC.mm.1AEG** at. the mnnuzucauring
contra* plan whi.cn thould be followed in tha
Chamises Association, '1225 Connecticut Avo., N, VJashingtor., D.C. 20009.
event of an accident. 6.4.1 Capacitors
C.2 K-.t.ionrl r.-..-r-.io-sc Center. O. 2.1 '.'-t is it l.oc..taon: 0.5. Coast ouard auadquartors,. Massif builerng, 400 /tn Street, S.V7. .. on ington, D.C. 20590
ci*.r/.i: Vo coordinate pollution emergen-- cios v/nen national involvement as requires. N. r.'-'icrti~r Network for receiving jjOiittion reports. Tne basis or this ..ot-- work i- a wull publicised toll-free tolo-
Capacitors should be installed in accordance with 3.7.3.
6.4.2 Yroncfomera
Transformers snould ho installed in accordance
with Section 4.2.3.3.
C.4.3 Spills
In cuso of liquid spills due to leaks or
cquipmor.t failures, tha procedures outlined in
sections 3.7.2 for capacitors and 4.2.3.2 for
transformers should be followed.
pi.o.iw number (u00--424--Cm,u2^ waica anyone
may use to call tho National Response Cen
ter reporting pollution incidents or acci
dv.nta vnaca may result m pollution.
i
.. .V"'r c '
-'-"lo rm to the local .
representatives of tho fcaerax Agency ro--
sponsible for action when s pollution dis
charge hub ,occurred. When necessary, otner
specific local, regional, or national rep
resentatives for tho variousagencies will
also be notified,
6.3 "hi"n'e of Lift Ids and Ec.-aipmcnt Con-
3.1.1 v r-VTiy 7.11 containers and equip ment containing PCbs shall be labeled in accoraanco win* sections 3.6, 4.1.s, a.22.1 and 4.3. 6.1.2 Ehi-T'irc Pnoors. Shipping papers should contain the following warning state-
CANY10": Contains PCSs(askarel) that are
e.ivirbvm.sntax contaminants. xn case or
leaks, or spills, restrain discharge, DO
_.. >. .* o.. iiu. cncr instructions caxl
Chwntrac (200-424-9300) and the manufac-
* 1 "
X?n + r* "* .* ^ f>rt firmn cn
7 REFERENCES
7.1 References to Tent
'
(1) Standard Method of Test for Rapid Gas
Chromatographic Estimation of High Boiling Eomologeos of Chlorinated Biphonyls for Capa citor Askar els, (ASTM D33Q3-74).
(2) American National Standard Method of Test for Spocific Gravity of AsJcarulo, C59.1965 (ki973) [ASTM D 1810-63 (1973)).
(3) American National Standard Method of Vest for Neutralisation Number by Color-Indicator Titration, 211,131-1964 (R1974) [ASTM D 976-64' (1973), I? 139/65).
(4) American National Standard Method of Test for Neutralization Number by Potcntioructric
Titration, ZU.59-19S8 (R1971) [ASTM D664-53 (1962), I? 177/643 .
(5) Standard Method of Test for Density of Rubber Chemicals,[ASTM D IS17-66 (1972)).
(6) American National Standard Kothod of Test for Inorganic Chlorides in Askarels, C59.55-1963 (R1973)[ ASTM D 1821-63 (1973)).
(7) American National Standard Method of Test for Pour Point of Potroluuro Oils, Zll.5-1966 (A1972) [ASTM D 97-66 (1971) , IP 15/67)).
(3) American National Standard Method of Test for Power Factor and Dielectric Constant of Electrical Insulating Liquids, C59.22-1967
(R1973)[ ASTM D 924-65 (1973)).
;'
739457
NEV 026202
/7
WATER PCB-SD0000056944
\y) iCu'.i Nw'cionvix tui'iuui*c* i*oc<iOCk oc V-sc i!o;- Specific iiuiistinco (resistivity) oZ Electrical 2a..elating Liquids, C55.51- 1555
[ twV. D 1159--51* (x9/u)) .
:1G) American Mi.txor.al Gtunduxd t'iCuhow or
Vest for Eydroxyrablo Chlorine Compounds in Chlorinated Aromatic iiyarocarbons (Asknrei) cdy.iOG-iyvoi.-djvi; d 1220-55 (I97i)].
(..!} /.r.urxcuA ..etaoaa1 Shanaard 2.c'.e.oa of 7w~.t ror VAcr.r.v... 5ai-o**)a*---ecy or Cnlox xx.atuc.
..ror.atxc r.yax'ocamons (Asxaroxc) , CSS *11" 197 0 l ,4**-*VV D .,5.>u--0*. :19 / x ^ )
(It) MMarrcoi'i ituiror>ul Scumubiau Method or C i' ( .. U_ JibvBBAihUVXUtl O ^ JvOuS X ..A V, , / o y013 19 /4 I AST.'. b25--/2).
(II) A:.._rican National Standard Methods of
Vesting Electrical Insulating Oils, C59.2-
/'i Awi,,( u rx /1 (x9 / a /
(I..) ixtiorrcvia i4utXGnax Stanc*.*xci i'.cchoc: or Vest ror e/xc...ectrxc> ErooxGc,v.rA Voxtagu or Insulating Liquids Using Dish Electrodes, Ce5 1 5--..5vo i*\x5/3, [ ..LT.*. D C / /~u7 (x9/xy)..
,
Dii, .u.-.orxcan i.atxonal Standard .'.othoc* or 7l-- ror* ,'Vu./ii and dire romts oy Cleveland
Open Cap, M11.C-1&73 {AS772 D 92-74, IV 3S/C7J.
(to/ Ai.v.ricun ..atxonal Stanunru Motnoc* or 7..-..Vi for Eayboj.t Viscosity, 211.2-1955 (To.971)
.iVeV*', a Cb,--si, vxi/u)) .
(17) 7_..ericar. national Standard Method of
VeJi ror Coerrrcrent or Tnormal Expansion of
Electrical Insulating Liquids of Petroleum
Origin, ana Askarels, C59. 57-1953 (1973)
(.'.JVM D 1903-53 (1973)3*
(It) 2.U..C.2# Av I,a Measuring the dissipation
-Actor, c.rox-ccuric constant, and resistivity at liqv.ru.,. "r.r.ulatior./Cxrcuits, vol 15, Mar. 197I, pp 40-49.
(19) Chlorodiphcnyls. Hygienic Guido Sorias. '.hv,tv,D'.vc, '.ww Jersey: American Industrial
..y.j.e.'.e Association, eun--2eb 19u5.
(25) Standard Specification for Chlorinated
Aromatic, hydrocarbons (Askarels) for Trana-
.u.V,c.i,,t
u 2xoo-- /*.]
7.2 C-.-.-VT.-1 Arfc-cncos
.
Polychlorinated Diphenyls and tho Environment, xAt.-recpartmcntal Vac,, dorco on PCos, Warn-- ington, D.C., May 1972. (National technical 2ndor.nation Service, U.3. 'Dept, of Commo-ca, .,p ringrrole., Va. 22151.) (CO.*.--72--X0*19).
DM.lvEh, C.a. Further observations or. tho
possible sy-tcmic toxity of certain of tho chlorinated hydrocarbons. Journal of Indued
f.l iYcirc and Toxicology, vox 21, x939,
4 J J3
*
DMIM'EEF., C.K.j WARREN, M.F.; AD2D SENNET, G.A. Vha probiux of possible systemic, effects
xro... c '.lorxnatca nyc.rocarbo*".s, Journal of ir? a.l }'"<!ier.c and Toxicology, vox x9,
iV h*"H
EL2C2NS, 12.B. The Chemistry of Industrial Toxicology. Maw York: John Wiley s. Sons, Inc., 1955.
G.eEENliURG, L.; MAYERS, M.R.; AND SMIT22, A.R.
Vho systemic effects resulting from exposure
to certain chlorinated hydrocarbons. Journal
of Industrial Hygiene and Toxicology, voiZ
21, lyjy, pp yy-iuT"
^
Threshold Limit Values for Chemical Suhstances and Physical Agents xn the W~o~f)~
roo.Yi Environment. Cincinnati: American Conrercnco or Govormental Industrial Eygior.ists, 1973.
TIcEON, J.F.; CLEVELAND, F.P.; CAPPEL, J; and ATC22LSY, R.W, The toxicity of the vapors
of Aroclor 12.42 and Aroclor 1254. American Industrial Hygiene Association Quarterly, VOl. 17, 1956, p? 294-211
S. REVISION' OF AMERICAN NATIONAL STANDARDS RE FERRED TO IN THIS DOCUMENT. When tho American National Standards referred to in this document are superseded by a revision approved by the American National Standards In stitute, Inc., the revision shall apply.
NfcV 026^03 .'
739458
WATER PCB-SD0000056945
(Vnusu Appendixes ai'i) not a part of American National Standard Guidelines for Handling and Disposal of Capacitor - and CraneTM ' rormar-Grado Aa#care^e Contammg Poj.ycniormafod Biphenyls , C107.1 -107 , but are included for information purposes only.
APPbHDIM A
Disposal Services
.
' '
.(g) Richmond Sanitary Service
Richmond, California (415-234-3304) All forms.
in addition to tho supervised dry land fill aims that may bo used for the disposal of askard-containing scrap, the following additional mown facilities ana corvicos have boon established. For other facilities, call your regional Environmental Protection Agency Office. (See Appendix D).
2. Chemical Waste Disposal Co.
Elizabeth, N.J. (201-351-5460) Disposal by incineration
.
3. Chcm-Trol Pollution Services,. Inc. P.O. 2o:c 200 1550 Balmor Road Kodol City, N.Y. 14107 Phono; 716-754-8231
Can handle solids and liquids by incinera
tion or land disposal.
The firms listed below (not all-inclusivc)
will accept PCDs for treatment or disposal,
as noted. Che V'r.droy-.mr/m-l Protection
." / v' dor': not >v.nr>r;;c r.'.v'' of those i:irj.a
* 'aovith r.or tho onviror.mrital
' ' ' o': o'Jc.'.Mtions. bach of ae.iO rrm*e nos nocn conractoa ana reports
n.tV^ng uno rogurrcc. tccnnzcal c..usuctc.>xs--
tic- to adequately handle PCLs, in accord
ance with r.ucoiW.sndcd Procedures for the
Disposal of ?CL-Contaning Waste (indus
trial Facilities) as published by EPM in
tho T:.5. .`.calstnr, Tho _appropriate
Gut.to or --FA nag'senar Office snouid bo
consulted far environmental suitability
or 'me farm/arte.
.
This organization has facilities and ser
vices capable of handlings
(1) biquids. Askarels alono or mixed with solvents or oils. Disposal by Kigh-temporaturo incineration.
(2) Solids (software). Askarel-soaked com pounds, .rags, cartons, absorbing earths, etc. Disposal by incineration or scientific landfill.
. (3) Solids (hardwares) . Capacitors, trans former tanks, core's, askarol-soaked metals. Disposal by scicntizic landfill. Has solvent extraction capability.
1. Cal:.:~o-:nf.a Clans " Landfills
(a) eternalia Disposal Site danta barbara, California (3G0-959-47Q3) Ltxx -repuras ane drummed nutormis.
vb) \ corporation Wilmington, California (213-775-3607) All farms.
(c) bnviroraontul Protection Corporation ..-'.her..'sraid, California
v (d) County of Dos Angelos
- '.'..itticr, California (213-559-7411)
. Facilities: Palos Verdes Calsoacas rf k*X aOihlMWt
. (e) Can Diago County
S..n Diego, California (714-555-5703)
.Ml forms
(f) Mntura County Dept, of Public Work3 Ventura, California (805-648-2717)
Am ror.us.
4. Hyon Waste Management Services, Inc. Chicago, 111. (312-645-0016)
Can handle solids and liquids by incinera
tion.
5. Monsanto Company 000 Worth Lindborgh Boulovard St. Louis, Missouri 63166
Phones 314-694-3352
Handles only liquid askarels manufactured
by Monsanto. Disposal is by incineration.
This organization has facilities and ser
vices capable of handling aakarel liquids alone
or mixed with othor oils or solvents by high-
temperature incineration. Liquid is pumped
through a gun with atomizing steam into incinera
tor .
`
NEV 026,(0^
739459 WATER PCB-SD0000056946
cuzu uUix*Yc.ai.nut* Ck\i 2000 *. waba
w.I'.-yU.'ui <juu, licit
aru c;uc;i-
C'Cu 'CO 1 ou^i' by COA'taCt Vi.wi Va'CCiT* GAG is
Liiw/t
*C * *jkTOVifj A a hig/*" Qi*0** gy VO*vUli
u c*rviaaoz iOi* irc-aovai Ox pa*rbxcu.lab&Ge ijOx^ro CHaUU'C. X. Ly *tIC aX.VT (ixV,, >o.xj*t gQUCG C&2TQ pUu**C;Cft
UTOTGUC/Yi u pGC.CCC* COllOun GCITUbhClT to xCiOVO
4Cl Auivairox xxcjuxgu coiYCGxrxr*g xaoitg their*
x*w i/u'CL* # ca any pao>}piicbU G&tGicG carnot ao
^CCtw^CUUa
C Aacxcair ag xao oy ;a*<j Co* p Inc LouJivilio, UY. (bG"42u"7IuO)
^'uCxii'CxCJ LiaO'x'xlOxCi r xxl faoci'c*cy / in"ov
l^iopouul. by luaUxxxi-j Car* handlo qiruxoaod
m,v u!kU>j UUU OOaXCi!i
buc.lt..*. or L'LyoAuoiriAc/ Corapuay ;ju,'< Cw`M\ DUYl,Gio*i 2*0* boa a'iO
,ijir....v-u.uf by* #-G35X ?bu;v..; oO v-VC4"00il
yucl.-.-.r LiUvir.o.-riAO* Cc^par-y
Di. :ub Division
b'..u*biuiu* Xbi. G1341
?ttOitw ' wib--v3 V"L3*S<
Yho octjunizatio'n provides containerization/'
urunaporccxon t unu Gxcpoaal services or alx
LicUxu** e* uO**uJ (xAClUCtXAg ijwxdWai'C) * DZZ"*
pea-1 i*> in controlled chemical and eciontific
lnuJill -rou. Licensed by Atovaic Hr*orgy
CoM-:.is-ion ror radioactive waste disposal*
V;,v organisation also aaa two West Coast loca
tions r in tha states of California and Waohin-
V. LoMin;: L/r/iro**z\cntal Cervices/ Inc .
2*0. bo;; 2340
,
Wilmington, Dolnuuyo 19C99
lionet 320"uSl"C541
.
Ynas organarauxon nas racialties and ser
vices capable o2 handling; .
(1) Liruids, Askarcl alono or rained with*
rolv^naa or oil:;. Liaposal is by high-texaper-
utti'u incineration
{2/ Soii&d (software). Aakarcl-soakcd coiiI>ovii.uuf irugn r cantons, ubiioi'bmy cartha, ot.c. Disposal is by incineration at combustion tu.-
peaturoo up to 2500 F. Incineration gases are scrubbed, and entrained Bolide are removed be fore exhausting to air.
Rollins Environmental Services maintains dis
posal facilities in the following areas?
Philadolphia/Camdens Hollins Environmental Services, Inc. Route 322 Logan Tovr.ohip "
Bridgeport, Now Jersey 06014
Eaton Rouge ?
Rollins Environmental Services, Inc. Scenic Kigh\;ay a West Cheatham Lane Scotianovillo East Eaton Rouge Parish, La. 70007
'
Houston;
'
Rollins Environmental Services, Inc.
Tidal Road a Highv/ay 134
Deer Park,Texas 77536
C. Texas Ecologists, Inc.
Robe-town, Texas
.
Phone: 512-307-3513
Disposal by landfill..
9. Wes Con, Inc. Twin l-'--llo, Idaho (206-733-0397)
.
' Receive packaged materials for dispoonl
ir. missile silos.
'
10. Gcdco'r Environmental Protection Cor?.
1313 Newburgh Rd.
Westland, Michigan 4C185
Phono> 213-326-0600
.
.
Kill accept transformers, capacitors and
PCBs solidified in Imbiber* beads.
APPENDIX S
ANALYTICAL PROCEDURES AND LABORATORY SERVICE
ORGANISATIONS.
Bl. General
.
'Analysis for PC3 in environmental samples
is a tedious process duo to the very low levels
(ppb or ppt) which are of interest and due to
tha high uonsitivity of the electron capture
chromatographic procedure. It cannot bo over
emphasized that extreme care must bo taken to
ensure first that the sample is representative
and second that sufficient numbers of blanks,
Dow Chemical Cor?.
NEV 026205
739460
WATER PCB-SD0000056947
1`GpxXCntUii aZ`Q tOStod tO bfciZXr.a
DORUSTIC
uu'b-Cw Ctatjw^^wy ^XlwXtS and preCISXO'A OU tiiS
manufacturer
particular equipment and procedure being used
Asuaxol*
Universal Mfg. Company
I
Cleanliness of sampling devices and contain" ota* and tncxr extraction is niso important
Chlorcxtol Clorinol
Clorphcn Diaclor
Allis-Chalmcrs Spraguo Electric
JARD Company, Inc. Sangarco Electric
Analyticai procedures for the determination
Dykanol
Elemcx
Cornell Dubilier MeGraw Edison
of PC.,x in air , watot ana sediments ax*o given
Eucarel Ilyvol
Electric Utilities Corp. Aerovox
in section La
Inerteen No-Fiamol
Westinghouso Electric Wagner Eloctric
Pyranol
Genoral Electric
L2. T-">ti::-.:toric
Sef-T-Kuhl
Kuhlman Electric
`tor a listing of laboratories offering survicus for PCD analysis refer to Directory of 'footing Laboratories publication STP333A available from the American Society for Tost" mg ana materials vAST.**) 1916 Raco Street, Phiiaaeipnia, Pa 19103* lx an outside
OFFSHORE
Clopher* Fonclor
Kenncchlor Phonoclor
Da
Pyralcna Pyroclor Solvol
Daycr (Germany) Caffaro (Italy)
Kcnncclor (Japan) Prodelec (France) Caffaro (Italy) Prodelec (France)
Monsanto (UK) USSR
x**oox'k*tory is usee, a vurxrxcatxon of capabxl*
i^cy ii* ^rccoututoriCtCcL
13. ',r,ai,v:r cr.i Procedures
I
*v;orlu-Wido gencx*ic name used for insulating liquids in capacitors and transformers that usually contain PCD's.
sou abt.*. D3s0m"/4* "Analysis of snvizGn--
APPENDIX D
mental Materials for Polychlorinated Diphenyls
ENVIRONMENTAL PROTECTION AGENCY REGIONAL
OFFICES.
/*PFjuiO.a v* T*\AD **',*Cu\ bnSaGNATxGNo USED oY KANUFACTUR'
f*w FOR QLIjuS CONTAINING PC3s * Capacitors or transzormozs xn service *nd
liquid shipments showing the following trade* -..-.ark designations contain PCBs. Those have been or are in uso and usually the designa tion appears on the nameplate or the warning
it*ncx
HAVE
Arcelor Ax*ocioz E Asbestol Askarcl* Auxarel*
DOMESTIC
MANUFACTURER
Monsanto Mallory American Corporation Hcvi-Duty Corporation Forrahti-Packard Ltd.
H
Environmental Protection Agency Region I, Room 2303 John F. Kennedy Federal Building Boston, Kassachusotts 02203 Telephones 617-223-7265
Environmental Protection Agency
Region II, Room 909
25 Fedci-al Plaza
New York, Now York 10007
Telephones 201-548-8730
'
Environmental Protection Agency Region II Curtis Bldg., 6th a Walnut Sts. Philadelphia, Pa. 19106 Telephone; 215-597-9398
Environmental Protection Agency
Region IV
1421 Peachtrea Street, K.E.
Atlanta, Georgia 30909
Telephone: 404-526-5062
Environmental Protection Agency
F.egior. V
230 South Dearborn Street
Chicago, Illinois 60604
Telephone: 312-896-7591
; . . NEV
026206
739461 WATER PCB-SD0000056948
L.,u. j. Protec iron agency
A ..Lion vx, 'Muj.'cu luGG
1000 POt `ComOA StTCOt
vcm-^ ysiOx
::nviiroA..;:.ntuI Protection Agency
.'; ,:gion Vrr
'
1 / u 0 mcuiXiiOre Avonuci
City, Mincouri 041C3
Velcpiiono: u^C--3 /l~j / /C
Lnvironir.mtoi Protection Agency
lienion Vi XX; Suite 000 10GO Lincoln Ltrout LAvAver, Colorado C0200 Vu luenonc: juo""0o/"*JoG0
Lnvironr.ontal Protaction Agency
Legion I." _
100 t Lilt comm S ti tv u
Guii L' LUiiCXiiViO f Liii XlGhiXlL
941x1
LAvironrental Protection Agency
Legion X 1200 Si:; th Avenue Seattle, Ytauhington 93101 Ve it. t pnonc a 0 w*4l2*12*io
NEV 026207
739462 WATER PCB-SD0000056949
ABSTRACT
This document presents the findings of a study of available wastewater management and treatment technology for the purpose of determining toxic pol lutant effluents concentrations and daily load achievable in three industrial categories: polychlorinated biphenyls (PCBs) manufacturing; capacitor manu facturing; and transformer manufacturing.
All plants in the above categories have PCB discharges to eithet water
ways or sewage treatment plants, under normal operating conditions. All
plants have discharges to storm sewers or directly to waterways under heavy
rainfall conditions.
,
Extensive survey of wastewater treatment technologies and cooperative laboratory work with several suppliers of treatment equipment and research facilities has confirmed that carbon adsorption technology is the best current candidate for successful removal of PCBs from the wastewaters. As an alterna tive uv-odonation was considered. This technology is still in the research stage; however, it offers potential of complete destruction of PCBs all the way to 002, water and HCl.
Another adsorbent technology new in the development stage, AMBEKLITE polymeric adsorbents, has demonstrated a PCBs removal efficiency roughly equivalent to carbon during laboratory tests. Further testing is needed with this adsorbent to accurately assess its potentiality.
For scrap oils and burnable solid wastes generated at these plants, high temperature, controlled incineration offers a straightforward method of de struction, whereas scientific landfilling appears to be the best suited mode of disposal for nonbumable cxntaminated solids.
Zero discharge objectives can be best achieved by eliminating discharge streams and developing recycle systems. All non-contact cooling water would be segregated, cooled, and recycled. All other wastewater streams would be pretreatecU The portion of the pretreated water which would be used in ` the plant would be treated with carbon, while the excess water would be
i.
NEV 026208
739463 WATER PCB-SD0000056950
incinerated in a specially designed system wiiich would allow for energy recovery.
Supporting data, rationale for the selection of above reoctmended treatstent technologies and associated costs are contained in this report.
. . NEV 026209 rr.
739464 WATER PCB-SD0000056951
VIII. REFERENCES
1. Hutzinger 0, Safe S, Zitko V: The Chemistry of PCBs. Cleveland, The Chemical Rubber Co Press, 1974, pp 3,4,7-9,22,23,197-220,243-48
2. Mieure JP, Hicks 0, Kaley RG, Saeger VW: Characterization of Polychlorinated Biphenyls, in Proceedings of the National Conference on Polychlorinated Biphenyls, November 19-21, 1975, Chicago, EPA560/6-75-004. US Environmental Protection Agency, Office of Toxic Substances, 1976, pp 84-93
3. Kuratsune H (ed): 'Environmental Health Criteria for Polychlorinated Bi- and Terphenyls--WHO Environmental Health Criteria Programme (Japanese document to World Health Organization). Fukuoka, Japan, Public Health Association, Japan Environmental Agency, 1974, 159 pp
4. American National Standard: Guidelines for Handling and Disposal of Capacitor- and Transformer-Grade Askarels Containing Polychlorinated Biphenyls, ANSI C107.1-1974, New York, American National Standards Institute Inc, 1974, 35 pp
5. Leardini T: The properties of askarels and recommendations for their use in electrical equipment. Study Committee No 15, Working Group 02, Cigre' No. 35:11-31, 1974
6. Ugawa H, Nakamura A, Kashimoto T: Studies on a calculation method for polychlorinated biphenyl Isomers (PCBs), in New Methods in Environmental Chemistry and Toxicology--A Collection of Papers Presented at the Research Conference on New Methodology in Ecological Chemistry, Susono, Japan, November 23, 24, 25, 1973. Tokyo, International Academic Printing Co Ltd, 1973, pp 253-67
7. Jensen S, Sundstrom G: Structures and levels of most chlorobiphenyla in two technical PCB products and in human adipose tissue. Ambio 3:70-76, 1974
8. Tas AC, de Vos RH: Characterization of four major components in a technical polychlorinated biphenyl mixture. Environ Sci Tech 5:1216 18, 1971
9. OECD recommends restricted use of polychlorinated biphenyls. Eur Chem News, March 2, 1973, p 21
10. PCB family of chemicals found presenting a threat to man; law proposed to limit use, impact. Commerce Today, May 15, 1972, pp 29,30
11. Tas AC, Kleipool RJC: Characterization of the components of technically polychlorinated biphenyl mixtures--II. Bull Environ Contam Toxicol 8:32-37, 1972
EXHIBIT
166
905411
WATER PCB-SD0000056952
12. HIrwe SN, Borchard RE, Hansen LG, Metcalf RL: Gas-liquid chromatography--Mass apectometric characterization of Aroclor 1242 and 1254 components. Bull Environ Contain Toxicol 12:138-44, 1974
13. Saeki S, Tautsui K, Oguri H, Toehiaura H, Haaana Ms [The isolation and structure elucidation of the main components of Kanechlor-400 (chlorobiphenyls).] Fukuoka Acta Med 62:20-24, 1971 (Jap)
14. Sissons D, Welti D: Structural Identification of polychlorinated biphenyls in commercial mixtures by gas-liquid chromatography, nuclear magnetic resonance and mass spectrometry. J Chromatogr 60:15-32, 1971
15. Webb RG, McCall AC: Identities of polychlorinated biphenyl isomers in Aroclors. J Assoc Off Anal Chem 55:746-52, 1972
16. Willis DE, Addison RF: Identification and estimation of the major components of a commercial polychlorinated biphenyl mixture, Aroclor 1221. J Fish Res Board Can 29:592-95, 1972
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