Document q6QVLo7zOw5kqxE0xqe7EZok

con kc PROCESS FOR THS PRODUCTION OF AROCLORS, PYRANOL3, ETC. AT THS ANNISTON AND AT TM WM. 0. iDTOWUCH PLANT April 1955 ..........----------- E. tether Distribution. List (amended July 19, 1956) 1. Hr. J. S. Brough, London 2. Er. N. B. Dyson, Newport 4 Newport T.I.2. file 5. Mr. 0. 7.`Taylor, Newport 4. Mr. 0. 7. Taylor, Newport # Newport Process Superintendent 5. Mr. V. Z. Hamer, Ruabon 6. Mr. J. F. Stiekley, St. Louis 4 Krumarich Plant 7. Mr. J. F. Stiekley, St. Louis 4 St. Louis Library 8. MCL file at St. Louis 9. Mr. D. B. Hosmer, Anniston 10. Spare held In M.C.L. file at St. Louis 11. Dr. V. A. Hayward's file Ruabon also Section II, Specifications and Test Methods, to Newport Analytical Department. WATER PCB-00049665 VI. PROCESS IN DETAIL, contd. VI - 3 Proses: Detail Packing The finished Aroclcra are run off Into drums, a piece of diape~ cloth being tied on the pipe outlet for the lighter Aroclors, and a piece of fine gauze for the heavier Aroclors, which have to be handled hot. This, of course, is to arrest stray bits of pipe scale etc., but the precaution is now omitted at the Krummrich plant when materia, are being filled' directly from the delivery of the filter. Newpo: arrangements for filling and weighing drums are discussed in Londc Engineering Pinal Report, September 1951/ page 1D8 and 1 F3-10, also in the start-up reports, July 24, and September 27, 1951. The drums must be clear, and dry, especial care being needed with electrical grades. Newport complaint NF/61, November 1951, of turbidity in 1248 was traced to the presence of water in the drums Apparently, in presence of water, the Aroclor reacted on the galvanizing of the drum, Newport plant report, December 1951 mentions the Installation of equipment for drying the drums. Care is taken not to do any packing if there is HC1 fume in the ai The gaskets for the bungs of the drums have to be correctly chosen A sample of the gaskets supplied by the Meiratn Supply & Gasket Co to the Krummrich plant was sent to MCL, April 1947. See also the ,n-(Jiftcuaaioa ^o-f.wgaak4a^on^paga.*2p^Seelon* IST-y-^be-l-cw--.' - Mr. Pemberton, December 1950, collected samples cf the labels used at -the Krummrich plant; cne a patent list label, and the other a warning label on toxicity. The effect of exposure of Aroclors to metal contact is discussed ir Section VII,' comments, page 17 below. Generally speaking, the dietilled Aroclors are packed in galvanized drums, the undistilled ones in black steel drums. Flaked or milled solids were packed in barrels or Leverpae containers, bulk solid or resinous Aroclors go out in friction type lid drums, (galvanized for the distilled grades). Storage and blending of the distilled Aroclors is done in steel vessels sprayed with tin or zinc, or aluminhm lined. A DM. 0C2 5 rononrn 47 i WATER PCB-00049666 VI. PROCESS IN DETAIL, coned. Packing, eontd. VI Proof Deta: Since the Aroclors are such effective solvents , they damage, ar.c are damaged by, ordinary paints, lacquers, Insulating varnishes,*' This feature is important In connection with hydraulic fluids containing Aroclors. See, for example, MCL Research Progress re" 1151, DP 5V26/7 and DP 5V277/6 and 1152 DP 4/16/7 and 8* July IS etc., also the Section III, Physical & Chemical data, above. Dru for electrical grades cf Aroclors are not painted. Newport Plant Technical Committee meeting, April 14, 1953, page 2 reported some promising teats with lacquered drums for electrical grades. It was decided not to use lacquered drums for resinous Aroclors on a returnable ba3ia, because the lacquer suffered at the high temperatures likely to be used in melting the material f: the drums. Aroclors also are dispatched in rail car3. At the Krummrich plant the manhole of the car is protected by a tarpaulin tent during fll Newport plant report for July 1954 mentions the installation of tank-filling facilities. The Krummrich plant operating instruct! August 10, 1954 mention that rail cars for Pyranols and Aroclors are Insulated and have either a steam coil or a steam Jacket. The are lined with Aluminium or else sprayed with tin and zinc. Only dry air Is used for unloading. MCC have a "Christmas Tree" fitting a one piece fitting carrying air valve, dip pipe, release valve^^ ,, _ andk...ftE.3 suce--gauge^>:Lfor--*Mte' on era-dr1* "t artkS'.* c^Tt'*d:s' to" `bra: the coil or Jacket of the rail tank in cold weather. Galvanized or lacquered drums are used for Pyranols. t:.OOOOH8 ACM 0C2 48 WATER PCB-00049667 XI. HAZARDS. Toxicity XI Hazar Ther i many literature references*to harmful effects of f of "chlor acne" resulting from exposure to chlorinated d<-^e-yls^ especially in cases where people working with small electrical c- ponents have been exposed to the fumes of hot, highly chlorinated Aroclors. Chlor acne is sometimes accompanied by gastric troubles" and there are literature references to liver troubles. *' There was some trouble of this kind among the production workers . Anniston in the early days of the development of the Aroclors. a that time highly chlorinated Aroclors were being made from diphen; which had come from low grade benzene. Since good benzene has bee used, the same Aroclors have been made without trouble. In March It was reported that the Anniston diphenyl and Aroclor plants had 12 years without lost tine accident. From the start of Aroclor manufacture at the Krummrich plant the operators have been supplied a clean change of clothes every day, and time has been allowed at the end of the shift for bathing. Operators are advised to wash hands and face before eating. The Anniston operators do not have the same issue of clean clothes. * Percy May, "Chemistry of Synthetic Drugs" , 3rd edition, page 1 The "Chemist Analyst", September 19^7, Volume 3, No.2 page 33 on the toxicity of diphenyl. _ ,(new edition) , ., J MCC Bulletin P-1^/mentions Oo to 1.0 mg. per cbm in air as th highest safe concentration of higher Aroclors, and 10 ng. for more-highly chlorinated Aroclors. Ho B. EdJdna "Chemistry of Industrial Toxicology", page _-9 giv< 0.5 to 1.0 mg. as the allowable limit in working rooms. The MCC Bulletin "Physical Properties of Aroclors" mentions sys temic effects arising from the oral injection of Aroclors, See the letters, E. Mather to P.J.C.Haywood, December 17, 1551, Mather to Newman, January 8, 1952, reviewing the literature on ' toxicity of Aroclors. See also correspondence relating to the article In Chem. & Dig. May 17, 195^ pages 2038 and the warning labels menti^ed on page VI-34 above. ACH CO WATER PCB-00049668 XI. HAZARDS, contd. x: Haz. St. Louis, Main Office Mr. P. J. C. Haywood Newport (Airmail) : Mr. w- E- Hamer, Ruatc Mr. w- H. Ritchie, Rua Dr. H. R. Newman, Ruab Mr. S. M. Kulifay, Kru Dr. D. S . Weddell, St. Mr. P T. Marshall , St December 11, 1951 AR0CI0R5: .'TOXICITY Since writing to you on December 3rd I have come across a letter of mine to Mr. W. M. Cooper, London, June 24, 1948, (copies to W.D.S., W.H.G., and others), calling attention to an article In the J. T. Baker Company's "Chemist Analyst", Volume 26, No. 2, page 33, September 1947. I attach a copy of this article, and I think you will agree that the warning relates only to really bad exposure, not such as should occur in ordinary analytical work. On October 27* 1947 Mr. Barbre of the Krummrich plant sent a copy- of the Journal to Dr. Jenkins at Anniston for comment. Dr. Jenkins did not make any comments at the time but the following extract from Mr. Barbre's letter is inter esting: "During the 11 years of production here only one man evidenced dermatitis. He had al3o shown similar symptoms in several other departments. When making Aroclor #1270 which Is flaked, a noticeable amount of fine fume solidifies In the air. If men are exposed to It during hot humid weather, the skin Is irritated, but we have not had any difficulty in curing cases of dermatitis from it" F,oooo40 ACM So E. Matr.er ( WATER PCB-00049669 XI - HAZARDS, contd. XI Kaza: The Chemist Analyst, Vol. 36, No. 2, page 33, J. T. Baker Chemical Co., Phillipsburg, n. j[ September 1947 ON THE TOXICITY OP TH2 "AROCHLORS" (sic) Robert M. Brown, Chief Industrial Hygiene Section, Division of Health Dept, of Public Welfare, City of St.Louis, Mo. _ A recently published article (Maglio, M. Martin, Chemist Analyst, 35 S2*- (19^6) ), has recommended the substitution of one of the "Arochlors" as the melting-point bath liquid in preference to the customary sulphuric acid. As stated in that article "Arochlors" are a group of chlorinated diphenyls produced by the Monsanto Chemical Company. There is need therefore to give warning. For the toxicity of these compounds has been repeatedly demonstrated, both from the standpoints of their absorption from the inspired air, as well as from their effects in produ c-ing a serious and disfiguring dermatitis when allowed to remain in contact with the skin. Since these effects have been repeatedly observed, industrial hygienists have taken care to see that the proper controls have been established wherever these products are used. For example, the maximum allowable concentration of chlorinated diphenyl for ' an 8-hour working day Is 1 milligram per cubic meter of air. It is probable that nothing like an uncontrolled industrial expo sure will occur -in the laboratory. However, whether an individual is subjected to a possible acute exposure to chlorinated diphenyl, . and its serious consequences, will depend upon the size of the Halting-point bath, the caution with which it is used, and the temperature to which it may be heated. Likewise, with careless handling of the material and the resulting contamination of the skin, clothing, laboratory towels, work'table surfaces, etc. the way is left open for the producing of dermatitis. Scrupulous cleanliness must be insisted upon wherever this material is handlec X The foregoing remarks have been prompted by the belief that in re - commending the use of a material with which is associated a potent! hazard from the health standpoint, it is very important that the possible consequences be presented together with recommendations fc correct handling. E000041 51 ACM CC WATER PCB-00049670 XI. HAZARDS, contd. XI Kazc Mr. A. C. W. Pennington of Newport, reporting on his tour, December 29, 1950, page 5, writes: can *` ` "ffiALTH AND SAJETY"; "At Anniston, no special protective clothing i3 provided the Diphenyl and Aroclors operators. A dally change of clothir was provided in the past but this practice ceased before the wa Gauntlet leather gloves and face shields are, of course, avails as required on the plant. " Tins of cold cream ointment, theatrical quality, are tc in the building, but the application of the cream is left to th operators decision of the Job in question. The men are expects take a bath, in their own time, at the end of the shift. A goo quality soap, and alcohol for rubbing down purposes, are provld The operators are sufficiently trained in the need for personal cleanliness that a record of bath taking is not warranted. ' "Emergency showers are provided on each floor of the Diphf building and safety notices are widely used. "At St. Louis, Plant B, the Aroclors building is rated a toxic department. Each operator is provided with a complete set of clothing comprising hat, coat, trousers, combination under clothes, socks and rubber shoes. A clean change of clothing, except shoes, is placed in the operator's locker in time for the following shift. Men working extra shifts are given a clean set of clothing. Canvas gloves and goggles are provided and 'Ply' hand barrier cream is available for use when necessary. "Twenty minutes' paid time is allotted for bathing at the end of the shift but, again, no record is kept that baths are actually taken. Theoretically, food is not allowed to be eaten within the Aroclors building. Instructions are issued that hand: and face should be washed well before eating. "Employees in to.-JLc departments are given an - annual medicai examination and a lung X-ray every three years.". monoA2 52 AC,, 0 WATER PCB-00049671 XI. HAZARDS, contd. x: - Kazar Toxicity, contd. A good deal of work has been done on detent!nation pressure of the Aroelors, and on the determination of/concentra- of Aroelors in air. See pages 9-, Section III, above, for"a *sum of this work. In 1950 (letter April 20, N. P. Rapps to E. Mather) the Admiralt; expressed interest in the determination of micro-quantities of Aroelors. MCC have a method for the determination of traces in air by means of the "Halidometer". Mr. Ellenburg, March 15, 195^, mentions work done by H. B. Richa: Jr., of MCC, June 17, 1953, on the determination of the concentrs of Aroelors in air. Mr. Ellenburg also states: "------------ work on the safe limits of Aroclor vapour concen tration in air is being carried on by the Medical Department at the Kettering Laboratories in Cincinnati. This work on animals is well under way, and will help us to know a little better Just what is the safe limit of Aroclor Vapours that one might work in." A question has been asked about the possible harm to plants if Arc containing paints are used in greenhouses. The reply is that most paints are somewhat harmful, and there is no evidence that Aroclor make them worse. Aroelors have been used as rabbit repellants, wi out doing any harm to vegetation. Care is needed in laboratories etc. where Aroelors are used in heating baths; there should be very positive ventilation. The vapours of hot Aroelors are distinctly irritating to eyes and ni above a concentration of about 3 mg per cbm in air. Newport plant report for December 1951 records bums by hot Aroclor -- a ease of a splash into a man's eye -- without serious damage. Packages of Aroelors leaving the Krurnmrich plant bear a label call attention to possible toxic effects. Ennooss c 1 A C f* C C WATER PCB-00049672 XI. HAZARDS, contd XI Haza Fire Hazards Diphenyl, of course, will burn, and reasonable care is needed in handling it. Precautions with toluene are mentioned also on pa~e VI-29< and under "Special Risks", below. 6 The Aroclors are handled as if non-inflammable. Drums of rateria are melted in the middle of the operating building, by open gas" flames, and open gas flames are freely used to heat pipe lines. An instruction, dated April 28, 1948, calls for a dally inspectioi of safety showers, fire extinguishers and gas masks, a check list being provided. Flanged Joints on Aroclor heating system can be a source of fume. See the notes on gaskets, page 2, Section XII, below. Phosgene may be generated in electrical flashes and fires in trans formers containing Aroclors, but thi3 is not thought to be a major risk. Safety Equipment Each operator in the Krunnrich Aroclor plant is supplied with gogg.1 rubber covered gloves, canvas gloves, rubber shoes and fume respire See also page XI-1. A spare suit of clothes is kept In a case in t N .-*ba^the-*tfsuai --cabir.^^/^'gaS^ms (chlorine), fir extinguisher, (toluene, diphenyl), stretcher, safe showers, drinking fountain, eye bath. Special Risks ' The usual ear is necessary in dealing with chlorine, in lighting the gas furnaces, and in handling hot materials, steam lines etc. Diphenyl might start to bum in chlorine gas if conditions in the chlorlnator were badly out of line. A Davis "Vapotester", model M-l*. Type A, (Division of Davis Emergen Equipment Co., Inc., Newark, N.Jj is held in the department for us. in testing the air of the working building after tciuer.e has been used, and for testing vessels before men are permitted to enter, an: before "flame certificates" are given. The instrument contains a Ennno44 ACM C0< 54 WATER PCB-00049673 XX. HAZARDS, contd. XI - 7 Hazard. Special Risks, contd. _ catalytic cell electrically heated to a fixed tempera fore, and th air to be tested is aspirated through it by means of a "squeeze ball". If combustible vapours are present, the temperature of th cell rises, and the Indicating thermocouple registers on a cali brated scale. The instrument has a zero adjustment, and it is checked twice a month by the Instrument department. Flame certificates must give the number of the Vapoteater used, also the data of its last cali bration by the instrument department. The instrument has been use ful in detecting gas escapes, and in tracing spills of gasoline, etc., from a neighbouring oil refinery into a public sewer which runs under Monsanto territory. Mr. Benignus, of St. Louis, September 1953, discussed the dangers of using Aroclors in indoor paints. He discounted the possible dangers from phosgene formed by flash discharges in transformers charged with Aroclors. See the references to safe handling of glycldyl phenyl ether on pages IX-161 etc. Y - .** . ^ 3k W-.. f--'----*>- k ~3r '< -X. FOT)00^5 AC" 55 0C2 WATER PCB-00049674