Document zdLQoz364N6L33xBn28JoXyaz

R&S 110905 9 UTH CHARLEST UNION CARBIDE CORPORATION CHEMICALS AND PLASTICS P. O, BOX 8004, SOUTH CHARLESTON, W. VA. 25303 Subject: Tribukh et al "Working Conditions and Measures for their Improvement in Production and Use of Vinyl Chloride Plastics" Giqiena i Sanit. (10) 38-44, 1949 Dear Bob: The subject paper has been repeatedly cited as evidence of the early incidence of vinyl chloride and polyvinyl chloride toxicity. Other sources have stated that the author concluded that the toxic effects came from the plasticizers used. In an effort to clarify the discrepancy a copy of the original article in Russian was obtained and retranslated. The translation does not clearly attribute cause and effect to anything. The authors'- conclusions are as follows: 1. Organo chlorine compounds, hydrocarbons, hydrogen chloride and carbon monoxide are given off during the fabrication of PVC plastics. 2. These cause irritation of the mucous membrance in the upper respiratory tracts. Dusts and vinyl chloride resin vapors cause dryness and atrophy of the mucous membrance and cause chronic bronchitis over a long period of exposure. 3. Changes in worker upper respiratory tracts and hepatitis indicate the need for further health research. 4. Use of sovol (diphenyl chloride) as a plasticizer causes acne type skin injury to workers. 5. Protective clothing and showers should control the skin injury from sovol. 6. For cleaner work atmosphere the decomposition of PVC must be reduced and a rational ventilation system provided. R&S 110906 The authors are aware that diphenyl chloride and chlorinated naphthalenes (sovol and golowax) attack the parenchemal organs (parenchymal refers to distinguishing cells of an organ-not too clear). Severe toxic effects are acute and sub-acute yel.low atrophy of the liver. They make no connection between this knowledge and the worker hepatitis. Other items of note are: 1. The specific process source of the PVC resin is not identified except that for shoe soles. Emulsion PVC is used for molding shoe soles. This type of PVC would be quite dusty and low in residual vinyl chloride monomer. Because of the widespread use of emulsion process PVC in Europe during this time it could be reasonably assumed that al1 the PVC used was made by this process. 2. The identification of potassium stearate as a stabilizer is in error. This is a soft soap probably used as a lubricant and non-stick agent. The stabilizer was probably some form of basic lead carbonate. No mention is made of pigments, fillers, etc. used which would contribute to dust and to toxic effects. 3. Neither diphenyl chloride (sovol) nor chlorinated naphthalenes golowax are good plasticizers for PVC. Dibutyl phthalate is tbe primary plasticizer. The other materials were probably added to the DBP to cheapen the cost or to get certain properties in the plastic. 4. The authors attribute the presence of organo chlorine compounds in the processing fumes to cleaved molecules of vinyl chloride (PVC-?) in different quantitative chain compound compositions. Boettner et al (Analysis of the Volatile Combustion Products of Vinyl Plastics) reports the major organic compounds given' off during combustion pyrolysis of PVC are benzene and*toluene with no condensible organo chlorine compounds. 5. Sampling and analytical techniques were not very sophisticated in 1949. Reactive gases such as hydrogen chloride and carbon monoxide could be accurately determined but the detection of* hydrocarbon gases was based on the condensation of the material with ice or dry ice thus there could be no entrapment or measurement of very volatile hydrocarbons such as ethane, propane, butane or vinyl chloride. - If organo chlorine compounds were truly collected and identified they must have resulted from the chlorine containing plasticizers in the plastic. My own conclusion is that this study should not be related to any vinyl chloride or polyvinyl chloride health effects. . The translation was done by A. 0. McCormick Company, P.0. Box 187, Dunbar, West Virginia 25064 not by Union Carbide Corporation. RNWJr:ke cc: J. W. Whittlesey Very truly yours, R. N. Wheeler, Jr. R&S 110907 | 5 i i t f 00003 WORKING CONDITIONS AND MEASURES FOR THEIR IMPROVEMENT IN ''^3 PRODUCTION AND USE OF VINYLCHLORIDE PLASTICS. Tribukh, S.L., Tikhomirova, N. P., Levina, S V., Kozlov, L. A. Gigiena i Sanit. (10):38-44(1949) The production of vinylchloride plastics and also the different goods prepared from them gained in the last decade considerable importance. In the meanwhile from hygienical point of view, it was little studied. The basic raw material for the preparation of vinylchloride plastics is vinylchloride resin, which is prepared from vinylchloride, a colorless gas, condenses at 12 - 14 in liquid with a specific weight of 0,86 - 0.9C Vinylchloride, on its turn, is prepared by the reaction of gaseous decompc sition products of petroleum vapors (vinyl) and gaseous chlorine. Sub sequently, the vinylchloride condenses by using dichloroethane and is sub jected to polymerization in autoclaves. In this way, polyvinylchloride resin is the product of vinylchloride polymerization. Due to th rjist- ance to alkali, diluted acids, ethers, benzin and lubricating oil,poly vinyl chloride resin is used for the preparation of acidresistant fillers, fabrics for overalls, substituents to hides, etc. At the preparation of various goods, the polyvinylchloride resin is plasticized with complex ethers of phthalic acid (dibutylphthalate), phos phoric acid (tricresylphosphate), mixture of diphenylchloride (sovol), or chlorinated naphthalenes (golowax). The selection of the plasticizer de pends on the assigned use of the plastic.to be prepared. According to the data of the literature, vinylchloride belongs to wea narcotics. Its narcotic concentrations for humans are within the limits . of 75 to 250 mg/1. According to the data by Petropavlovskii (1942), vola tile substances, liberated, when vinylchloride resin and plasticizer^^re heated to I3O-I650 cause in animals under the condition of one single inocculation, depending on the concentration, the following phenomenal R&S 110908 . irritation of the ocular mucous membrane, respiratory, disorders, damage of ; he central nervous system, breakdown in the coordination of movements, and death, after appearance of asphyxic convulsions. Sovol and golowax, .introduced into vinylchloride plastics, as plasti cizers, have general and local toxic effect. In their overall action on the organism, sovol and golowax are close to chlorinated fatty hydrocarbons. Basically they attack the parenchemal organs. Severe toxic effect takes place in form of acute, or subacute yellow atrophy of the liver. In the literature, cases with lethal outcome are described, caused by the toxic effect during the production with vinylchloride naphthalenes (golowaxj. and diphenyls (sovol). The local action of sovol and golowax causes acn -type skin eruptions and erythematous-vesicular dermatitis. We studied the working conditions at the finishing of vinyl chloride plastics under factory conditions in a vinylchloride plastic plant, using vinylchloride plastics as substituent for hides and for insulation of electric wires. Production of vinylchloride plastics- In the vinylchloride plastics plantj the vinylchloride resin (a white powdery mass) is mixed with dibutyl- phthalate, or with sovol in mixing apparatus, at a temperature of 80-100. Then, the compound is transferred onto rollers, the surface of which is heated to 130-l60V. At the end of the rolling, the vinylchloride fabric is cut up in nar row tapes, which are further sorted and packaged in boxes. 30 1 -3- R&S 110910 During the hygienical inspection of the vinylchloride plastic plant, the air of the working place was examined on its sovol-.organochlorffci compound-, and hydrochloric acid vapor content.' The obtained results are plotted in Table 1. Table It- Organochlorine compound, sovol and hydrogenchloride cont nt in the air.of vinylchloride plastic plant i Ko.meaTpaa o a ui,,i HuBBHite oTieaenna / MeCTT B3BTHB npeJn z xjopopraHH- iccK.ie.coeau- He no. a tom auc.ie coaoa 3 CL x.iopacrufl BOJOpO} 3 it nojroTOBirrejbaoe j^B tcKiJij* noz-rrpeaa U. T* ; COttOJl ............................... !jj B cepiiii.ie noveuii Ha tr Cuetuento n J Ba.IbU, JHtClt , ypodHi 'sixa.iiu piJjwro Jo y cx;HTd.ia BO 3pM i CMemejns tcoM.io.tf.tTOi . . 6 To ace jJl y CHiCHTsja bo 3pesa 1 8Urpp3 aOMnOiHQ'ia . . . jtt. Ha piloxeti tcecis sxib| uodtn tki............................. ,/3 y ctczi aoa oiiyaaiiaero noaciHiun "J Caepdoaot-ioe jU y pifowro HiCTa caep- jioataeci 'I 0,003 t:>- He oC.iapyaceu 0.003 : 0,06--0,08 | 0,0j3 C,Cl--0,08 /q"He oOHapyatsa 0.2--0,97 l 0.00.! 1 0,27 is - He oCitapyviceu 0,005 | * 1, Name of the department; 2, Place of the sample taking; 3* concentra tion in mg/1j 3a. organochlorine compounds,included sovol1; 3b* hydroger chloride; h-. preparation; 5* mixing and rolling; 6. the same; 7* dril ling; 8, in the exhaust hood of the heated sovol; 9. in the middle of the chamber, at the respiration level of the workers; 10. at the mix r at-the time when the components were mixed; *11 .`-at the mixture, at the time when the components were discharged; 12. at the working place of rolling; 13 at the deck for the cooled plastic compound; 14, at the working place of the drill operator; 15. not detected;. In the air of the working places of the vinylchloride plastic plant, as one can see this from the data of Table 1, the concentration of organo chlorine compounds fluctuated between 0,005 to 0,27 mg/1. In the prepara tion department sovol vapors formed at its heating, discharging and trans portation. The concentrations of organochloride compounds, found in this place (0,005 mg/1) can be attributed, most likely, in great part to sovol. ^ On account .of the insufficiently developed method to determine sejSRatel organochlorine compounds, they were determined summarily. t the mixers the organochlorine compounds were found in an amount from ' 0,01 to 0,08 mg/1, and in the working place of the rolling - from 0,2 to 0,97 mg/1. In the product sorting' department the organichlorine compounds, usual ly, did not exceed 0,05 mg/1* We detected hydrogenchloride only in the dif ferent samples in amounts, not exceeding thousandth - part: of milligram. In connection with the use of sovol, soiling the skin with ingredients in the composition of which sovol was introduced causes serious danger. On the skin of the hands of the workers we found organochlorine compounds. To fight the contamination of the air, the plant was mounted with influent and exhaust ventilation with automatic driving. The exhaust ven tilation was constructed on the principle of local exhaust from the hood?, placed over the basic sources of gas evolution. The efficiency of the ventilation, as this was demonstrated by the sanitary-technical inspection,was insufficient, on account of th fact,that the air-feed was carried out with a rate of only 7-8 m/sec on th level of the shoulders of the workers. The unpleasant sensation, caused by si milar way of air feed, together with the'infiltration and cooling f the compounds on the rollers forced the workers to overlay the damper of the sprinkling valves and already with this, the air current, escaping through the different leakages, decreased the work of the exhaust device, deviat ing the convective current, which got up from the rollers. 3esides, the closing of the influx nozzle, disrupted the balance between the influx and the exhaust and attracted inorganized admission of contaminated air from the neighboring places. ......avvaa 1**.,**..... IiI R&s 110912 A significant defect of the ventilation system was the insufficient efficiency of the low-capacity hoods, arranged over the decks for the r^^y products and over the mixers. Much more effective are, according to our project executed orifices over the mixers in form of tents with open front wall (see the figure). At a productivity of 1 000 m^/hour these orifices practically completely localized the separation of noxious gas. f Scheme of the tentlike openings of the mixer. Use of vinylchloride plastics as substituent for hides t- In the pro duction of vinylchloride footwear, the .basic raw material is polyvinyl chloride resin, which is prepared by the polymerization of vinylchloride in a water-emulsion method'. The temperature of the decomposition of this resin is 130 - 150. As plasticizer here dibutylphthalate and as stabiliz er potassium stearate is used. The compound for the sole is prepared by mixing textile scraps, sa turated with dibutylphthalate, and vinylchloride resin in the mixer. The obtained compound is piled on the heater to L?0 - 200 and rubbed through, after this with Vaseline in the press mold. The, in this way filled ^ess form is closed, it is maintained for a few minutes, and then is placed for a short time under the hot press.  The composition for the upper footwear is obtained by mixing a deter mined amount of polyvinylchloride resin and dibutylphthalate in the mixer. The mass is kept there for aging 12 hours at a temperature of 70. After the aging the compound.is rolled at a temperature of 120-1^0 with the ad dition of potassium stearate. The vinyl chloride plastic compound, obtaine after the rolling is rapped in textile and pressed at a temperature of 160 The analysis of the air for noxious gas and vapor content in the plant of vinylchloride footwear production is plotted in Table 2. Table 21- Concentration of gases and vapors in the air of working places 5n vinylchloride footwear manufacturing plants in mg/l MeCTO B3BTH8 npo6 A y UJMIOB . . y npeccos . . `Xjopoprawne- i CXHt coeAHHeuHa " Hn |7 C 1 (cyMuapHo) CO 6 KOHaeHTpaana a xr/.i 3. 5 : 1= ^ I3. S == 3 * tXs *i : kX 3 w : ! s= ai XX W* *XU X msj* mX 5* X *oOQ, 3 (3 :!is r* l" i xx 9I: <5 7Z xx Io&- is5DSx*3;!1xSrjxsa s 5- .i . ij 0.14 0.48 0.33 0,028 0,036 0,032 0,07|0,33'0,2: . 0,022 0,26 1.13 0,65.0,008 0,036 0.053 0,212.611.23 0.019 B nouemeHHH enapoiHofl 0,33 : 1,2 0.92 0,03 0.17 0,23 0.100.6S0.23 0,01 ! DO 0) o <0 CO 1. place of the sample taking; la. at the rollers* lb. at the pr ss* lc. at the welding place*2.organochlorine content* 3. minimum* 4. maximum 5. average* 6. concentration in mg/l* 7. total. The organochlorine compounds, which evolve at the thermal finishing of vinylchloride resins, represent cleaved molecules of vinylchloride in dif ferent quantitative chain compound compositions. In the air of the working places at the manufacturing of vinylchloride footwear, we found these com pounds in an amount from 0,14 to 1,2 mg/l. Here we found also vapors of hydrochloric acid in concentrations from 0,008 to 0,17 mg/l, hydrocarbon vapors (determined summarily) from 0,21 to 2,61 mg/l and carbon monoxide |/apors within the limits of 0,01 to 0,022 mg/l. * i The contamination of the atmosphere by organochlorine compounds and vapors of hydrochloric acid increases in proportion with the tempera increase at the heating during the different manufacturing operations. The ventilation of the working place was carried out by means of a fe' exhaust devices, originally destined for local exhaustion. In spite of thi comparatively " high frequency of air exchange (10 - 20), the effi ciency of the ventilation was insufficient. Its basic imperfection was thi lack of local removal of the gas, evolved during the work at the pressing rolling and welding of the footwear. The hood over the welding working benches, usually used in this kind of production, was not efficient and could not be considered as a local ex haust device, because at the welding of the vinylchloride footwear, the gases evolved-on the level of the knee of the seated welder, in the imme diate closeness to his face. A more radical device in the given case is a vertical exhaust channel against each working place. The removal of^^e air can be carried out through orifices in the platform of the working ben< the upper part of which, thus, should be used as planar, exhaust channel. Satisfactory effect can be observed also in case of exhaust through a horizontal box, arranged on the surface of the working bench. The rate or suction through the exhaust orifices should not be less than 6 m/sec. Use of vinylchloride plastics for the insulation of electric..wires t-> In the factory, where vinylchloride plastics are used as insulating materi; for electric wires, the covering of the wires with vinylchloride envelope, is carried out on extruders. During the time, when the vinylchloride plastic compound is dried in the drying chambers, and also at its fusion and at the discharge of the wires from the hot envelope from the head of the extruder, in the ai f the working space we found the following volatile substances (Table 3). R&S 110914 Table 3 MecTO ttsTna npofi b XJopopraHIKCCKHC coezjtdCHHa i ( to Ss -f 3* 51 Ua4t 3 mJ*3t HCl C (cyMMapHO) It KorfaeHipaauR , r/.i. CO i1 3 3* =* ' uaS3lat ^*= 3 3<3sS3 or 5S suat*tt*ttor-*rat 33 /||1. r3kz * --* 33 rt V*a* --323 y sinpKcwanni iu b soxe a jbixaaHs pa6oiero . . . Haa nposojsM. noicpuwu 6 ropaqefl luacruaccofi . . B cepeaxxe noMeiaeuxa/J Hxx cvmxxbHux miaifaoM n I0.C03 0,1 o.oo: 0,06 0,14 0,65 He o6xa< pyxeja 0.004 0,088 To 0.3 o, :o 0.14 0,016 0,08 0,6 t1 ii 0.017 0.05 * 0.11 i 0.02 0,24 j ' 1 _ 1. Place of -the sample taking; 2. organochlorine compounds; 3* concentra tion in mg/1; k, summarily; 5* at the extruder in the zone of the workers respiration; 6. over the wire, coated with hot plastics; 7. over the drying chest. 8. was ftbt tfeteetod? - 9. oiniiaum; / 10, maximum 11. in the center of the place. In the composition of the volatile substances, evolved at the heating of the vinylchloride plastics, up to 120 - 140, there is an organochlo rine content of 0,003 to 0,6 mg/l, vapors of free hydrochloric acid.from 0,001 to 0,06 mg/l, hydrocarbon vapors from 0,08 to 0,6 mg/l, and carbon monoxide vapors from 0,01 to 0,05 mg/l. The ventilation of the plant was accomplished by means of exhaust hoods, arranged on the telescopic downstroke over each extruder head. The gases, evolving at the drying of the plastic compound in the drying chest and at the cooling of the .vinylchloride wire after discharging from the extruder head, arrived in the atmosphere of the working places,maintaining in them a considerable concentration of toxic substances. Results of the medical examination of the workers- A randomly se lected group of workers in the inspected plant was subjected to medio^^ ex amination. In the vinylchloride plant 48 men were examined, mainly roller workers. At the rhino-larynx examination, in a great number of th . workers, in the upper respiratory tracts (in the nose, larynx, and thrache white films of 'dust were observed, which were formed as a result of th mixture of dust with the mucus. These films were compact at the touch and could be removed from the surface of the mucous membrane only with diffi R&S 110916 culty. In 17 men hyperemia of the mucous membrane of the upper respirator; tract was found. Chronic bronchitis was detected in 13 men. As to the change in blood circulating organs, one must mention vascular hypotonia (90 - 100/45 - 50) in 13 men, moderate hypertonia in one, arterio-cardio- sclerosis - in 5* The condition of the gastro-intestinal tract was charac terized in 10 examined workers by chronic gastritis and in 2 by chronic colitis. In 15 workers there were alterations in the liver in form more or less pronounced hepatitis, accompanied in 2 examined workers by cholecystitis. Regarding the blood, 29 examined workers had low hemoglobin count; on - 46$, 22 50-55^1 and 6 $6-60%, The blood picture and the ROE were with out peculiarities. One must pay attention to the skin diseases (acne, bleakheads), es~ # pecially on the face, the neck and the chest, found in the examined group. The skin injuries were found not only on the face of those who were in t contact with sovol, but also on those, who wers not in direct contact with it, but were working in the same place. Evidently, the skin disease was caused by the action of sovol, when its vapor was sorbed. In. the chemical plant 25 female workers were examined, mainly those, working at the presses and welding with a long working record of 3 - 6 years in the said professions. In some of them, examined for ear - larynx different degree of hyperemia of the mucous membrane of the upper respira tory tract was observed, on its whole extent, or only on the organic parts* Chronic bronchitis was found in 5 mildly expressed emphysema of the lungs in 3 and remaining signs of pleurisy in 2. As to the cardio-vascular system in 14 men vascular hypotonia (R/R 90 - 110/55-65) and in 4 mildly expressed hypertonia (R/k 140 - I65/8O85) was detected. Thudding sound of the heart, its enlargement and the data of the. ECGj. Low T-wave of heart, not less than by 2 basic abduction and the roundness of the S - T interval, gave foundation, in some cases, to diagnose distrophy of the myocardium. In the examined group, in 6 workers hepatitis was diagnosed. At the same time,in some persons,'.simultaneously liver and stomach disease was de tected. Not in one of the liver disease cases could we find in the anam nesis, or at the examination,signs of jaundice. Neither did we detect any bile pigment in the urine. In a considerable number of the examined work- rs small swelling of the liver, without characteristic pain and sensitivi ty at palpation was observed. Analyzing the results of the medical examination, one must remark, that in a known part of the workers, changes in the upper and deeper res piratory tracts were detected. These findings are confirmed also by the data of the literature. One must pay attention to the high percentage of skin injuries, which is, no doubt connected ethiologically to the action of sovol. The presence of hepatitis in some workers, in contact with vinylchlo ride resin and vinylchloride plasticizers deserves serious consideMiion Therefore further dynamic observations on the state of the health of the workers, who are in contact with vinylchloride resin and its plasticizers, are necessary, to prevent the development of severe liver damage*.. Results 1. - Into the composition of volatile substances, which form at th thermal finishing of vinylchloride resins and plasticizers, during th manufacturing organo-chlorine compounds, hydrocarbons, vapors of free hydrochloric acid and of carbon monoxide enter, 2. The action of these volatile substances are manifested in the ir ritation of the mucous membrane, mainly of the upper respiratory tracts* lengthy influence of finely dispersed dusts and vinylchloride resin vapor: cause, besides, dryness and atrophy of the mucous membrane of th upper respiratory tracts, and is also responsible for the development of nit R&S 110918 bronchitis 3. A considerable number of hepatitis among the examined workers, and also the change in the upper respiratory tracts, raise the question of the necessity for further dynamic research on the state of the health of the workers and to take a series of therapeutic-prophylactic measures, in particular by organizing heat and moisture* Inhalation of drugs for the workers, 4. At the use of vinylchloride sovol-, as plasticizer, on most worker acne type skin injuries, with preferable location on the face and neck, were observed, 5. For the prophylaxis of skin diseases at the work with sovol, the following complex sanitary measures have to be taken* 1) securing foor th) e; workers work underwear and outfit; T (alkaline) 2) construction of sanitary sho 4I with separate undressing for home and work cloths. At the sanitary pas sage, there must be a vapor chamber for the low temperature steaming of underwear and work outfit, at a temperature of 110-120^ for one hour. The plant should be equipped with wash basins with hot and cold running water. 6, For the sanitation, of the atmosphere, it is necessary to deer ase, as much as possible, the degree of vinylchloride resin decomposition at it thermal finishing. This must be attained by standardizing its heat re sistance, and also by controlling the temperature when the rollers, the presses and other equipment are heated, not to exceed 120-130, Of extremely great importance .is the rationally equipped ventilation system, calculated on maximum screening-off the source of gas-, vapor- and dust separation. In connection with the fact, that in some factories the inflammation of the condensate was observed, which occurred in the exhaust ventilation tubes in contact with open flame, the exhaust apparatus must be projected by observing the conditions, adopted by the construction legislation for construction , designated for the mixing of inflammable gaseous niix*fcures* \ 3J 99 (/) o CD to WORKING CONDITIONS AND HEASURES FOR THEIR SANITATION IN THE PRODUCTION AND UTILIZATION OF VINYL CHLORIDE PLASTICS S. L. Tribukh, N. P. Tlkhomlrova, S. V. Levin and L. A. Kozlov1 Translation of: "Usloviya truda 1 merogrlyatlya po Ikh ozdorovlenlyu prl protzvodstve I ispol'zovannl khlorvlrillovykh plastlcheskikh mass," Arg. Sanit., Volume 10, 19^9, pp. 38-A5- -- Ovex the last decade there has been considerable development of the pro duction of vinyl chloride plastics and of various articles of these plastics. Only little study has been devoted to this production, hqwever, from the hygienic standpoint. The basic raw material in the manufacture of vinyl chloride plastics is vinyl chloride resin, which is obtained from vinyl chloride, a colorless gas which condenses at 12-14 into a liquid having a specific gravity of 0.86-0.90. The vinyl chloride in turn is obtained on interaction of the gaseous products f decomposition of petroleum (vinyl) with gaseous chlorine. The vinyl chloride is subsequently condensed by use of dichloroethane and is subjected to polymeriza tion in autoclaves. The polyvinyl chloride resin is thus a product of polymeri zation of vinyl chloride. Because of its stability toward the action of alkalis, diluted acids, alcohol, benzene, and lubricating oil, polyvinyl chloride resin is employed in the production of acid-resistant washers, fabrics for pro tective clothing, leather substitutes, and so forth. In the manufacture of various articles the polyvinyl chloride resin is plasticized by esters of phthalic acid (dibutylphthalate), phosphoric acid (tricresylphosphate), and a mixture of chlorodiphenyls or chlorinated naphthalenes (Holowax). Selection of the plasticizer depends on the purpose of the plastic being manufactured. .: v According to data in the literature vinyl chloride is a weak narcotic. Vinyl chloride concentrations which are narcotic to man range from 75 to 2S0 mg/1. According to Petropavlovskiy (1942) the volatile substances evolved on heating of the vinyl chloride resin and plasticized resins to 130-165 cause the following effects in animals subjected to a single innoculation, depending on the concen tration: irritation of the visible mucous membranes, impairment of respiration, affection of the central nervous system, impairment of coordination of movements, and death accompanied by phenomena of asphyxial convulsions. The chlorinated diphenyl and Holowax introduced into the plasticized vinyl chloride resin as plasticizers have a general and local toxic effect. In their general effect on the organism the chlorinated diphenyl and Holowax resemble chlorine-substitution hydrocarbons of the aliphatic series. In the main they affect the parenchymatous organs. The course of severe intoxication is that of scute or subacute yellow atrophy of the liver. Cases have been described in the production Research Laboratory of the Institute of Labor Hygiene and Occupationa Diseases of the Academy of Medical Sciences of the USSR. -1- literature of fatal termination in poisoning during production with chlorinated naphthalenes (Holowax) and diphenyls. The local action of chlorinated diphenyl and Holowax is manifested in skin affections of the acneform and erythematous-vesicular dermatitis. We have studied the conditions of work with vinyl chloride plastics under plant conditions at a plasticized vinyl chloride resin shop, the resin being used as a leather substitute and for insulating electric conductors. Production of chlorinated plasticized resin. At the chlorinated plasticized resin shop the vinyl chloride resin (a white powdered mass) was mixed with dibutylphthalate or with chlorinated diphenyl in mixing equipment at a temperature of 80-100. The composition was then transferred to rollers the surface of which was heated to 130-160. At the end of the rolling process the sheet of vinyl chloride on the rollers was cut into narrow strips which were subsequently sorted and packed in boxes. In inspection of the plasticized vinyl chloride resin shop the pair of the areas in which work was done was analyzed to determine its content of vapors of chlorinated diphenyl, organic chlorine compounds, and hydrochloric acid vapors. The results obtained are summarized in Table 1. As is to be seen from the data given in Table 1, the concentration of organic chlorine compounds, ranged from 0.005 to 0-27 mg/1 in the air of the production rooms of the plasticized vinyl chloride resin shop. In the preparation department chlorinated diphenyl vapors w re liberated during heating, pouring and transporting of the resin. The con centration of organic chlorine compounds found in this room (0*005 mg/1) may with high probability be ascribed chiefly to the chlorinated diphenyl. Organic chlorine compounds were found in the mixers in an amount ranging from 0.01 to 0.08 mg/1, and at the roller operator's station from 0.2 to 0.97 mg/1. In the sorting department the concentrations of organic chlorine compounds -usually do not exceed 0.05 mg/1. Hydrogen chloride was found only in isolated samples, in amounts not exceeding thousandths of a milligram. As a result of the use of diphenyl a serious danger is represented by the presence of conditions permitting contamination of the skin with ingredients forming part of the composition. We found organic chlorine compounds on the skin of the worker's hands at the end of the work day. In order to prevent air pollution the shop is outfitted with forced air intake and exhaust ventilation. The exhaust ventilation is organized on the principle of local exhaust from hoods mounted above the main sources of gas volution. As was demonstrated by the sanitation engineering inspection, the effectiveness f the ventilation was inadequate because of the fact that the air was delivered t a rate of only 7-8 m/sec at the level of the worker's shoulders. The unP*aS3nt sensations caused by this method of air delivery, along with the swelling and cooling of the composition on the rollers, forced the workers to cover the slide valve of the sprinkler pipes, and even when this had been done the streams of air escaping through various leaks impaired the operation of the exhaust R&S 110921 ' system, deflecting--the convection flows rising from the rollers. In addition, closing of the intake pipes disrupted the balance between the inflow and exhaust and caused disorganized intake of polluted air from adjacent rooms. tABLE 1. CONTENT OF ORGANIC CHLORINE COMPOUNDS, CHLORINATED DIPHENYL, AND HYDROGEN CHLORIDE IN AIR OF PLASTICIZED VINYL CHLORIDE RESIN SHOP. Name of department Place of sampling Concentration, m'y/l Organic compounds, including chlorinated diphenyl^ Hydrogen chloride ; Preparation . Mixing and rolling Same * Drilling Chlorinated diphenyl heating cabinet Center of room at level of worker respiration At mixer during transfer of compositions At mixer during transfer of compositions At roller operator's posi tion At plasticized resin cooling At drilling operator's station a 0,005 0.003 0.06-0,08 0,08 0,2-0.97 0,27 0,005 None detected 0.025 None detected 0.002 None Setected 1 Commas Indicate decimal points. A serious defect in the ventilation system was represented by the inadequate effectiveness of the low-capacity hoods mounted above the finished product tables and above the mixers. Hoods above the mixers in the form of tents with the front wall open (see drawing) (produced i on the' basis of our design) proved to i be much more effective. With a delivery of 1,000 ra3/hour these hoods almost entirely localize theevolution of noxious gases. Use of plasticized vinyl chloride resins as leather substitutes. The basic raw material in the production of vinyl chloride footwear is polyvinyl chloride resin obtained on polymerization of vinyl chloride by the water-emulsion method. The temperature of decomposition of this resin is 150-150. The plasticizer employed in this case is dibutylphthalate, and calcium stearate serves as the stabilizer. 2Since the method of separate identification of organic chlorine compounds .has not been Adequately developed, here they were given a general identification. -3- R&S 110922 The sole composition is prepared by mixing cloth scraps impregnated with tributylphthalate and vinyl chloride resin in a mixer. The composition obtained is placed on a mold heated to 170-200 and afterward smeared with vaseline. The mold filled in this manner is covered, held for several minutes and then placed under a hot press for a short time. The composition for the uppers is obtained by mixing specific amounts of _ polyvinyl chloride resin and dibutylphthalate in a mixture. The mass is left here to age for 12 hours at a temperature of 70. After the aging the composition is rolled at a temperature of 120-140 and calcium stearate is added. . The plasticized vinyl chloride resin obtained after the rolling is transferred to fabric and pressed at a temperature of 160. R&S 110923 The results of analysis of the air for its content of noxious gases and vapors in the vinyl chloride footwear shop are presented in Table 2. TABLE 2. CONCENTRATION OF GASES AND VAPORS IN AIR OF VINYL CHLORIDE FOOTWEAR PRODUCTION SPACES, mg/1 place of tampling At toilets At presses In welding j room Organic chlorine 1 compounds HQ C . .(total) CO average maximum 1! .minimum maximum average 1 average m axi mini! 'm in im u1m 1 Concentration, mg, 1 6: E oC<3O j3 p S9* ITi E 'S' a p .. 5s 1 0,14 0,25 0.48 jo.35 - 0,023 0,036 Ml 0,0320,07 0,350.2: 1.13 jo,65 0,003 0,036 0.0550,21 2.61 1.23 0,022 - 0.019 0,53 1,2 0.92 0,03 0.17 0,23 jo.10 0.6SO.23 i 0,01 Commas indicate decimal points. % The organic chlorine compounds^eyolveri in^th^hgnr.^trearm^nt of vinyl chloride resin are detached-molecule^ of vinyl ^chloride- in various quantitative ^combinations of their chain comoounds. iv'e found these compounds in amounts" rarigihg from 0.14 to 1.2 mg/1 in the air of the vinyl chloride footwear pro duction rooms,. Vapors of hydrochloric acid were also detected here, in con centrations^- ranging from 0.008 to 0.1-7 mg/1, as well as hydrocarbons (ranging from 0^21 to 2.61 mg/1 (total determination] and carbon monoxide ranging from , 0.0J. to 0.022 rag/1. - Pollution of the ambient air by -ozganic_hl.orine compounds and hydrochloric\ acid vapors increase with elevation of the heating temperature in various production operations. * , Ventilation of the production areas was accomplished by means of several exhaust fans initially designed for local exhaust ventilation. Despite the re atively high air replacement frequency factor (10-20), the effectiveness of v*ntllati0n was found to be inadequate. The chief defect in it was the a scnce of local removal of liberated gases formed during treatment of the composition on the presses and rollers and in welding of the footwear. ; i / The hood installation above the welding benches usually employed in such production is not effective and may not be regarded as a local exhaust device, since during the welding of vinyl chloride footwear gases are liberated at the level of the knees of the seated welding operator in the immediate vicinity of < his face. The most radical installation in this particular case is a vertical . exhaust duct opposite each of the operator's positions. Air may be removed ; through an opening in the top of the bench, which in this case must be used as a blast exhaust duct. \ A satisfactory effect was also observed with exhausting through horizontal ducts placed on the surface of the bench. The rate of removal through the exhaust openings must be no less than 6 m/sec. \ \ Use of plasticized vinyl chloride resin for the production of electric conductors-! At the plant at which plasticized vinyl chloride resin is used as an insulating material for electric conductors, the conductors are sheathed with vinyl chloride on extruders. j / R&S 110924 The following volatile substances aTe released into the air of the production room during drying of the plasticized-vinyl chloride resins in the drying cabinets, and also while it is being melted and when the conductors emerge from the head of the extruder into the hot sheathing (Table 3). Place of sampling TABLE 3. Organic chlorine. compounds HC1 c. (total) Concentration, mp/l E3 E K<a4 E9 E a. 6 6 X<4 E CO m in im u m maximum m in im u m m in im u m maximun At extruder in area of worker respiration Above conductor sheathed in hot plastic In center of room 0,003 0,14 0.031 0.1 O.COI 0,0G 0.65 Not observed! O.OJsfc Ditto. { 0.3 -- -- 0.0 -- - -- 0.017 O.03 o.u -- Q,U2 Above drying cabinet 0,10 0,14 -- j O.Olfi 0,03 Commas Indicate decimal points. 0,21 -- -- I ti i' The volatile substances liberated on heating of plasticized vinyl chloride resin from 120 to 140 include organic chlorine compounds in amounts ranging from aCL03_t:o 0.6 r.c/l, vapn-r; of free hydrochloric acid in amounts ranging from 0.001 to u.0t> cg/1, hydrocarbons ranging from 0.08 to 0.6 mg/1, and carbon monoxide .ranging from 0.01 to 0.0S mg/1. Ventilation of the shop was accomplished by means of exhaust^elcaslf i on a telescoping lowering device above each extru er ea during drying of the plasticized resin in the drying i dSdurine cooling 1 extruder'head J f the plastic sheathing of the conductor after it emerges ^ entered the air of the production room, maintaining considerable concentrator .. of toxic substances in this room. v Results of medical examination of workers. Sample groups of workers from / the enterprises inspected were subjected to medical examination. In the plasticized I vinyl chloride resin shop 48 persons, primarily roller operators, were examined. Rhinolaryngologic examination revealed a white film formed as the result of S mixing of dust with mucus in the upper respiratory passages (nose, larynx, and trachea) of a large number of the workers. Such films were solid to the touch S! and it was difficult to remove them from the surface of the mucous membrane. Hyperemia of the mucous membrane of the upper respiratory passages was found in 17 persons. Manifestations of chronic bronchitis were found_in lajjersons. Among, i i the changes relating"to the"organs'of blood circulation mention should be made * of vascular hypotonia (90-100/45-50) in 13 persons, moderate hypertonia in one person, and arterial cardiosclerosis in 5 persons. The condition of the gastro intestinal tract was characterized in 10 of the persons examined by manifestations of chronic gastritis and in 2 manifestations of chronic colitis. In 15 persons there were changes affecting the liver, in the form of more or less pronounced hepatitis, which in 2 of^the persons examined was combined with manifestations of cholecystitisv As regards the blood, in 29 of the persons examined there were low hemoglobin figures: 46% in one, 50-55% in 22, and 56-60% in 6 persons. The blood formula and the erythrocyte sedimentation test exhibited no abnormality.. Attention is attracted by the fact that skin diseases (acne,.comedones) were observed in the group examined, especially on the face, neck, and chest. Cutaneous.} affections were observed not only in persons coming in contact with the chlorinated, i diphenyl, but also in ones having no direct contact with it when working in the t sam room. The skin diseases apparently were caused by the action of chlorinated * diphenyl absorbed in the form of vapor.. At the chemical plant 25 female workers were examined, chiefly press operators and.welders, ones who had worked in this occupation chiefly for periods ranging fr m 3 to 6 years. Various degrees of hyperemia of the mucous membranes of the upper respiratory passages, over the entire extent of the passages for only . over limited sections, were observed in some of these persons, who were examined by,an otolaryngologist. Chronic bronchitis was detected in S persons, moderately \ severe emphysema in 3, and residual effects of pleuritis in 2 persons. \ As regards the cardiovascular system, vascular hypotonia (R/R. 90-110/55-65) \ was observed in 14 persons and moderate hypertonia (R/R 140-165/S0-8S) in 4. The thudding sounds of the heart, expansion of its limits, and electrocardiogram data: a lower T-wave of no less than 2 basic deflections and grounding of the ST interval, provided a reason in several cases for a diagnosis of myocardiac dystrophy. ^ jfcpgtitis was diagnosed in 6 persons in the group examined. At the same time affciTtion of the liver and stomach simultaneously was observed in some persons. In none of the cases of affection of the liver were we able to find symptoms of jaundice in the anamnesis or on inspection. Nor were there any bile pigments in the urine. Slight enlargement of the liver, without the characteristic complaints and sensitivity to palpation, was detected in a large number of the persons examined. i In analyzing the results of the medical examination it is necessary to note that changes relating to- the upper and deeper respiratory passages were detected in a certain number of the workers. These observations are also confirmed by data in the literature. 6- R&S 110925 k* e ] Attention is attracted by the high percentage of cutaneous affections, which from the etiological standpoint are unquestionably associated with the action of ' the chlorinated diphenyl. Serious attention should--be-s-iv-en--to. the circumstance of the presence of 4 h*parry7s_jn_ ^-`<a-or-the workers coming in contact with the vinyl chloride resin ancPthe plasticized resin. Thus further close observation of the state of health of.workers coming in contact with vinyl chloride resin and the plasticized resins ' are required in order to prevent the development of serious affections of the . Findings 1. The volatile substances formed when vinyl chloride resin and plasticized r sins are subjected to heat treatment in production include organic chlorine jD compounds, hydrocarbons, vapors of free hydrochloric acid, and carbon monoxide. C/> 2. The action of these volatile substances is manifested in irritation of li the mucous membrane chiefly of the upper respiratory passage; protracted action by the highly dispersed dust, and vapors of vinyl chloride resin additionally ro causes dryness and atrophy of the raucous membrane of the upper respiratory 01 passages, and also contributes"towards the development of chronic bronchitis. 3. The considerable number of cases,,of_hepatitis .among the workers examined, as well as the changes in the upper respiratory passages, raise the question of the need for further close observation of the^tate_of healt-Jr-of"workers and the^taEIntPof a number of therapeutic., and .prophylactic,.measures, particularly rganization of warm humid (alkaline) inhalation of medicinal substances for workers. 4. With chlorinated diphenyl used as a vinyl chloride plasticizer, cutaneous affections such as acne, with predominant localization on the face and neck, were observed in the majority of the workers. ' S. The following array of.sanitation measures-is required to prevent skin diseases during work with chlorinated diphenyl: 1) provision of protective under- j wear and outer clothing for the workers; 2) insulation of a shower room of the sanitation control station type, with individual dressing rooms for street clothing and work clothing. The sanitation control station should be outfitted with a steam room for steaming these protective underwear and clothing at a temperature of 110-120 for an hour. The shop should be provided with wash stands with hot and cold water. 6. In order to sanitize the ambient air it is necessary to decrease as nich as possible the extent of decomposition of the vinyl chloride resin when subjected to heat treatment. This can be achieved by standardizing its thermal stability, and also by regulating the temperatures to which the rollers, presses, and other equipment are heated, so as to prevent the temperature from exceeding 120-130. Of extremely great importance is efficient organization of the ventilation system with the aim of achieving maximum coverage of the sources of liberation of gases, vapors and dust. -7- t i R&S 110927 In view of the fact that cases of ignition of the condensate form in the ventilation exhaust pipes on contact with open flame have been observed at some plants, in the designing of exhaust systems the specifications given in legislation governing construction for systems designed for the transmission of combustible gaseous mixtures must be complied with. -8- ** PO Box No 6 Bessemer Road Welwyn Garden City Hertfordshire AL7 1HD Telephone Welwyn Garden 23400 (STD Code 07073) Telex 264251 Fax Welwyn Garden 35556 (STD Code 07073) mjSBrial Chemical Industries PLC Petrochemicals and Plastics Division Professor C H Tamburro University of Louisville School of Medicine Health Sciences Center Louisville Kentucky 40292 USA cc Dr B Bennett ) + copy of Dr J J O'Sullivan ) Tribukh Dr A P Wright ) Dr M N Johnson File + copy of Tribukh Your ref Our ref JS/LJW/DSO-16 Tel ext 7535 Date 12 January 1983 R&S 110928 Dear Professor Tamburro VCM - ASL CASES Dr Tim Carter of BP has told me of his telephone conversation With you. I hope that you and Mrs Tamburro will have a comfortable flight and that you will enjoy your weekend in London. I look forward to meeting with you at the Royal College of Pathologists on Monday 24th and again on Tuesday 25th at 9.30 am in Conference Room 01, Imperial Chemical House, Millbank, London. When we are at the Royal College, I shall give you directions to get to IC House. I understand that you have an arrangement to go to Prof Scheuer at the Royal Free Hospital on Tuesday 25th after our meeting at ICI is finished. If our meeting lasts all morning and you can spare the time, my colleagues and I would be delighted if you would have lunch with us in our mess-room at IC House. Prof Jenkins has circulated the speakers' summaries. I was Interested to read your introductory sentence "In 1949, Tribukh et al first reported hepatitis like liver changes in vinyl chloride polymerisation workers". Dealing with translations from Russian papers is always a problem. I have usually worked on the basis of the translation of Tribukh made available to the industry by B F Goodrich (copy enclosed). If the translation is accurate, the work is not concerned with VCM polymerisation workers at all and the health effects described are not unequivocally attributable to VCM. The paper is concerned with PVC compounding and fabrication not .polymerisation. Though the work done was reasonably good for its time, VCM is not clearly identified, measured or distinguished from chlorinated diphenyls and naphthalenes. Residual vinyl chloride would almost certainly have been evolved from the heated PVC as it was being compounded. The paragraph under Table 2 on p4 asserts that the vapours were "detached molecules of vinyl chloride in various quantitative combinations of their chain compounds". Frankly I don't know what the authors meant to say and perhaps the wording suffers from translation and perhaps also a basic lack of chemical knowledge on the part of the researchers. PVC does not depolymerise to give VCM on being heated. Any VCM given off would be residual VCM in the PVC polymer. If my arithmetic is correct, 1,2 mg/litre is 1200 mg/mJ or 600 ppm in the footwear production rooms. This concentration of VCM is quite astonishing if it all came from residual monomer in PVC. My guess is that the authors could not distinguish between organic chlorine molecules (chlorinated plasticisers etc) and VCM and that the 1.2 mg/1 is not VCM pure and simple. 2- - Unfortunately the Tribukh paper has been abstracted wrongly, eg Abstract 505 pi15 of ORNL/TIRC-78/3 (Nov 1978) put out by your National Library of Medicine. Over the years I have given out dozens of copies of the BFG translation of Tribukh and invited people to read it in toto for themselves and to eschew inaccurate abstracts. I hope you will forgive me for taking up this matter of Tribukh in your summary but I would not want you to legitimise and perpetuate what I believe to be one of the myths in the history of VCM. With best wishes Yours sincerely J Stafford Health & Environment Protection 'i R&S 110929 Medlzlnischo Unlveralt&tskllnlk Dlrsktor: Profaaaor Dr. H. J. Danalar f** Mftdlzlnlachs Unlv*r#itAtoklInlk * Slgmund-Freud-Str. 28 9800 Bonn 1 Dr. J. Stafford Health <3r''lmvironment Protection Imperial Chemical Industries PO Box Bb>. 6 Bessemer Road Welwyn Garden City Hertfordshire AL7 1HD England j tfew*03/3 0300 Bonn i, 5th Slgmund*Frud*3tr. 23 Rufmimnw C03283 380-1 Oufchwohlnummar 280* T<ex 8800840 ktbo d March, 1933 33 C/3 O CD CO o Dear Dr. Stafford, Thank you very much for your long and detailed Letters of February 11 and 18, 1983, and also for your kindness to provide me with a copy of the epidemiological study of respiratory disease by SOUTAR et al., 1979, and the two other papers to which I, indeed, had no access at the time when my manuscript was ready for printing. I was glad to learn that you found my paper useful. In your first letter you raised a crucial question concerning TRIBUKH's early paper. Production (proizvodstve) of vinyl chloride resins is, indeed, only mentioned in the title and referred to in the opening and introductory paragraphs of this paper, but the 48 male workers examined were said to have'been mainly roller operators (prelmushchestvenno ;val*tsovshchiki). It remains unclear whether at this early period the"Chlorinated plastizised resin shop" was actually part of a PVC production (polymerization) plant, as the title of the paper suggests. It is also unclear to which plant the authors refer; from subsequent investigations of environmental conditions in PVC production carried out by SMIRNOVA (1954, paper mentioned by FILATOVA) and later by FILATOVA et al. (1958), I thought it likely that TRIBUKH's paper also dealt with the Gorlkii combinat where apparently all of the Russian work on adverse effects of vinyl chloride up to the present (see FILATOVA et al., Gig. Tr. Prof. Zabol. no. 1, January 1982, pp. 28-31) has been conducted. I used a photocopy of TRIBUKH's original Russian paper and since I have some very limited knowledge of Russian I tried to translate the article with the help of a slavicist from the Slavistic Seminar of our University, who, however, was not versed with the technical and medical terminology which I had to provide. From the English translation which you kindly sent me I can see, however, that the two translations are practically identical. You will have noticed that in my paper (see page 44) I accentuated that the group of 73 workers examined were "mainly engaged in PVC compounding". I interpreted TRIBUKH's statement that"the organic chlorine compounds evolved in the heat treatment of the vinyl chloride resins are detached molecules of vinyl chloride" to mean that unreacted monomer was released by the heating process (and we know well enough that in those early days PTC resins did contain considerable amounts of unreacted monomer, especially when the freshly polymerized resins were JO immediately used for processing without intermediate storage), fi I also accentuated that the authors "held other volatile com CO pounds derived from halogenated aromatic hydrocarbons (...) ... responsible for the systemic toxicity". o CD All this goes to show that I too had some doubts as to the 03 substantiation of the title's claim; however, I have not been able to unearth any earlier hint or warning from the world literature, weak as this one (TRIBUKH's paper) may have been. But on second thought I admit that you are probably quite justified to repudiate TRIBUKH's claim concerning production of FTC. For your information I include a photocopy of my original copy of this paper which was published in "Gigiena i Sanitaria", issue no. 10, October 1949, pp. 38-44 (not: "Arg. Sanit." vol. 10, pp. 38-45). I further include a photocopy of SKIRNOTA' s paper (Gor'kii combinat) who was actually the first author to describe occupational acroosteolysis in one fitter and two centrifuge foperators in 1961. five years before this type of YC-induced_ lesion. was recognrggtl~Tn Europe-^ " You also inquired about the AS1 case described in my paper in fig. .6 a+b (pp. 56 + 57). You were right, he did not die in June 1978 but on the 28th of August 1978, two days before we expected him to show up at our clinic to have a computerized tomography of the liver because during a short stay at our clinic in eafly August 1978 the clinical examination led us'to suspect -tfthat angiosarcoma of the liver was developing. His(A.W.) birthI&& I date was the 6th June 1937; these data, I hope, will make it (J^ possible for you to identify this case of A3I in your register (Bynamit Nobel). I apologize for the delay in answering your letters, but even today it takes me some time to formulate my words in a foreign language. With kind regards and best wishes. ficAsej2. tHiriALS p.0.8. -- - wy |7 Yours sincerely, Prof. Dr. W.K. Lelbach