Document rBkdddoG21LJGyn6Rmr553p5E

T7/ /S o o A STUDY OF THE HEALTH WORKERS INVOLVED IN THE PRODUCTION OF PENTACHLOROPHENOL AND OTHER CHLORINATED PHENOLS Department of Environmental Health University of Cincinnati Submitted by: Raymond R. Suskind, M.D September 29, 1980 A STUDY OF THE HEALTH WORKERS INVOLVED IN THE PRODUCTION OF PENTACHLOROPHENOL AND OTHER CHLORINATED PHENOLS Raymond R. Suskind, M.D. 1, INTRODUCTION During the week of October 1 - 5 , 1979, a medical survey of 115 employees of the Monsanto Chemical Intermediates Co., in Sauget, Illinois was conducted by the Department of Environmental Health University of Cincinnati. The objective was to determine the health status of em ployees of the W.G. Krummrich plant, who had been exposed to chlorinated phenois and to identify those conditions which might be related to the work environment. Pentacfylorophenol is a common substance which has been used for many years as a preservative of wood products, a preharvest defoliant, a pesticide for termite control and a general herbicide. Acute exposure at high concentrations may cause irritation of eyes and respiratory tract. There have been reports of accidental systemic intoxication which have been fatal. In work situations, prolonged exposure may r e s u l t i i i ^ ^ ^ acneform dermatitis which may become complicated by s l ^ ^ n t e l t i ^ j i ^ Ortho and parachlorinated phenols have been e m ^ J ^ ^ a i ^ j ^ St f e c t a n t s and bacteriostatic agents in a number of f ^ ^ j ^ r a o ^ i i ^ u s t r i a l uses. These uses have sometimes been associated w m f s^rrtation and sporadic allergi sensitization. t* 4 2. THE SCOPE AND CONDUCT OF THE SURVEY The medical survey included the completion of an administered questionnaire by the employee-participant, a medical history, a thorough dermatologic examination, as well as the examination of other organ systems, if indicated by the clinical history. Skin biopsies were done as well as cultures for bacteria and fungi when indicated. Clinical laboratory tests '---------------------- , included: blood, CA, P, BUN, Creatinine, BUN-creatinine ratio, uric acid, glucose (fasting blood sugar), total protein, albumin, globulin, total bilirubin, direct bilirubin, transaminase SGO and SGP, alkaline phosphatase, LDH, cholesterol, iron, magnesium, sodium, potassium, chloride, G-glutamyl- transpeptidase, trigylcerides and lipoprotein profiles; CBC and differential, ^irinalysis and urinary coproporphyrin, uroporphyrins, and^ creatinine. Si nee the" values for urinary coproporphyrin, uroporphyrins and creatinine were determined from a single void sample rather than the required 10 ml. aliquot of 24 hr. volume it was not possible to interpret significance of levels out side the normal range. A thorough review of records provided by Monsanto for^^^brtt information was carried out. These records included d i s p e n s a ^ i n i t ^ . ^ ^ a l exa mination records by plant physicians, m e d i g ^ ^ ^ i i ^ ^ ^ a i m s , workmen's compensation records, and personnel assignments. These records were particularly useful in confifi^g^jjjiiiiric information given by the par ticipants, i.e., personal medical hiftories obtained in this survey were com pared with physician notations which indicated previous physician recognition and medical care for specific problems, e.g., acne vulgaris, chloracne, hypertension, diabetes, etc. These records also provided additional information -2- not obtained through the questionnaire or during the physical examination. The population examined included persons who had worked in Building 236 in which pentachlorophenol was produced until April 1978 and/or in Building 237 where o and p chlorophenol was made. The total number of active employees who worked in these two areas was 157. Of these, 115 persons volunteered for this examination; 115 were interviewed and 106 completed the physical examination. The interviews were conducted by two experienced occupational health interviewers with nursing training and experience. 3. CHARACTERISTICS OF THE WORK AND WORK AREAS At the time of the survey employee-participants were working in as many as thirty-six departments. They included machinists, insulators, pipefitters,* welders, mechanics, painters, truck drivers, coal passers, service department personnel, warehouse personnel, operators, unit con trollers, carpenters, safety personnel, instrument mechanics-electricians, engineers, foremen, and product Their commonality was havir 237. 0 and p chlorophenol were *. Employees describe their wc Bagging, packing, drum or*drumming, prin or wonting cne p n u tower, working on the chlorinator, dryers, flaker, pouring molds or burning molds, working on the filter, working on the dissolver, making briquettes or working with the briquette machine and mixing or blending raw materials. According to Mr. P.E. Heisler the Plant Safety Director: Two products were made in the pentachlorophenol department: > 1) Pentachlorophenol or "Penta" and, 2) Sodium Pentachlorophenate or "Santobrite" ` Pentachlorophenol (Penta) Pentachlorophenol was produced by "chlorinating phenol" on the by-product mono.di or trichlorophenols. The reaction vessel was called a chlorinator. As first produced the pentachlorophenol existed as a molten liquid and had to be cooled and solidified in order to be sold. There were three ways to produce the solid product in a form which could be used by the purchaser: a) The material was "flaked", by feeding molten material into a container from which it was picked up on the * surface of a cold rotating drum. The drum rotated against a stationery blade which separated the thin film of material from the surface. This immediately broke up into small flakes which were conveyed mechan ically to a packing area. For sale the oroduef was "bagged" or "drummed" cylin- drical " f i b e i C s ' - .... b) The flaked matsrrar was superceded by "prilled" material In this process the molten material was sprayed into a stream of cool air where it solidified into spherical beads or "prills". The equipment used was called the prill tower. The waste air was "scrubbed" to remove "penta" before discharge to atmosphere. The prills -4- were cooled further in a 'Yotolouvre" cooler and conveyed mechanically to a hopper for packing into bags, fiber-packs or steel drums as was the . flaked material. The prilled material flowed more freely and was easier to pack than the flaked material but also escaped from the conveying and packing equip ment rather easily. This spilled material required regular clean-up from around the equipment. As may be expected, the prilling operation required careful con trol and even with the best operation the tower and air ducts became coated with material. Frequent cleaning was required and this was indeed a dusty and dirty job. Various coating techniques were iised to make prills which were "dust free", c) Some customers had facilities in which they could dis solve a large solid block of pentachlorophenol. Accordingly the molten material was poured into large Because of the^(ji5 ^nK^t|nj point of the material n^g^Sa^icUise1 torch to heat the mold ^ i^jn^BSurffing11 the molds. As the mold was. a small amount of "penta" vaporized from the --5- surfaces which had been heated. Sodium Pentachlorophenate (Santobrite) This material was made by dissolving pentachlorophenol in sodium hydroxide solution to form a solution of sodium penta chlorophenate in water. The solution was made in the "dissolver" and transferred to a "settler" to remove settleable impurities. It is.possible that a filter was once used for this purpose but there is no record of this. The solution was then sprayed into a "paddle mixer" which could have been referred to as a "blender". This formed a granular product which was then dried in a rotary drier and separated into "fines" and "pellets". The fines were fed to a "briquette" machine which compressed the material into tablets. As with the pentachloro phenol, the dry product in its various forms was transferred to hoppers, etc. by various mechanical conveyors and elevators and was packed into a variety of packages according to customer needs. Clean up of the material lost from conveyors, driers, mills, screens, etc. as well as clean-up of the equipment, was a requirement of the job. ' Emptying and cleaning o1 of exposure. 4. RESULTS The results of the survey and examinations are sumnarized in a series of tables (Tables 1 to 23). -6 All participants were informed that the results of the individual examinations would be made known to them through their personal physicians. Eighty-?five requested reports and these were sent out to physicians. Significant Clinical Observations As Indicated in Table 2 there was a fairly even distribution of workers in the age groups 21-30, 31-40, 41-50, 51-60. Sixty-six of 115 workers had a history of chloracne (Table 3). Forty-three were found to have residual chloracne and of these cases 67.6% was mild and 32.5% moderate. All of the residual cases were comedonal in type and 32.5% of those had cystic lesions as well (Table 3). Chloracne is most frequently characterized by comedones, cysts, pustules and papules, occurring on the cheeks, periorbital, temporal */ ! areas and forehead. Lesions are sometimes limited to the malar areas \, and hirsutism may first be observed on the malar sites as well. In some types of phenoxy herbicide chronic chloracne cases, elastic tissue changes, such as actinic elastosis, are observe :cur even at a relatively early age. ;ons were found to have malar hirsutq G k ,t wereo^hiOi^iiave actinic elastosis (Table 5). HoweverjVriiist of these were in persons who were both of light complexion and over 50 years old. Four of the 12 cases of actinic elastosis had chloracne. Of the 106 persons examined, 45 had a history of acne vulgaris and 22 or 20.7% had some evidence of acne vulgaris at the time of the examination. Of the 43 cases of chloracne 20 worked in Building 236, 22 worked in both Building J36 and 237 and a questionable case was - 7- found among the 6 persons examined, who worked in Building 237, only. This was a case offene vulgaris who appeared to have some characteristics of chloracne. In Table 8 it would appear that among workers exposed for more than two years there was a significantly higher number of cases of chloracne than those exposed .in less than two years. It should also be noted that all of these cases left the process between 1971 and 1978. Sixteen of those had residual chloracne of which 11 were mild and 5 were moderate. Clinical Laboratory Findings Of the eight skin cultures taken four corroborated the clinical impression of dermatophytosis. They consisted of three persons with T. rubrum infections and one with T. mentagrophytes infection. The laboratory data is presented in Tables 15-Chrough 22. 5. DISCUSSION ?& The populations surveyed consistea^grerirsons exposed to a pentachlorophenol manufacturing process or to the pentachlorophenol process as well as the ortho and para chlorophenol process. Since population exposed only to the o and p chlorophenol process, alone :was very small [8] a'riii it was not .possible to > , compare findings in the "penta" group with that of the o and p chiorophenols group. There appears to be no significant difference in the clinical and laboratory findings when the group exposed solely to the pentachlorophenol process [Building 236] compared with the group exposed to the combined -8- pentachlorophenol process ortho and para chlorophenol [Building 237]. In the analysis of laboratory data, possible correlations between the history of chloracne or residual chloracne and levels of test results were examined. A small number of evaluated total serum lipids were observed. There was no correlation between the serum lipids and the presence of chloracne. While persons with elevated triglycerides were found in both the chloracne >. and non-chloracne groups, there appeared to be no correlation between serum triglycerides in the presence or absence of chloracne. No significant differences in levels of cholesterol, LDL, SGOT, SGPT, and GGT were found t* between the chloracne and non acne groups. Several interesting statistic correlations were observed. Their sig nificance with respect to the risk of pentachlorophenol exposure is still to"be determined. The frequency of abnormal levels of VLDL was significantly increased in those persons with a history of chloracne or withj-^i^ikl chToracne as compared to those w h o 'never had chlo about 602 triglyceride. Another interesting observationToncantfi^thb''levels of HDL found in r*elation to persons with no history of chloracne, a history of chloracne and those with residual chlorance (Table 23). There appears to be less residual chloracne in the group with HDL level of 45 or more than those in the group with levels less than 45. Levels of 45 or greater are known to be indicative of average to low risk for coronary heart disease. There was also significantly less chloracne found in workers who do not smoke now even if they smoked previously, than those who currently smoke. In this instance there is the possibility that persons who smoke may smoke on the -9- rJ job and hands contaminated with material from the pentachlorophenol process may contact the face and forehands and-result in a heavier ex posure of those skin sites. It should be noted at this time that 24 participants in the current study had also worked in Departments 262 and 268 in this plant where esters of 2,4-D and 2,4,5-T were made. The ethyl, butyl, isopropyl and isooctyl esters of 2,4-D and 2,4,5-T were made in Department 268 and 2,4-D itself made in Department 262. The exposure periods very from less than one month in either Department to as much as 84 months in Department 268 and as long as 32 months in Department 262. The years in which these processes were in operation were: 1947 to 1970 for Department 262; 1962 to 1970 for Department 268. When the examination records of the twenty-four persons exposed to the above processes were analyzed, there appeared to be no significant difference in the frequency or severity of chloracne in these twenty-four as compared with those who were exposed to the processes in B u i M i M ^ 2 3 6 and 237. While the groups are relatively small it ditional exposure did not enhance chloracne.^ 1?g^ifeSilcPnot know if there were persons who were just (Bosses in Building 262 and 268 but not to the pentachlorophenol the para and ortho chlorophenol process. - 10 - We wish to express our appreciation to Mr. P.E. Heisler and his able staff, Teddi Marshalak, all of the nurses, for their invaluable assistance during the conduct of the survey. - 11 - TABLE 1 Participants Interviewed Examined Males Females * Black Hispanic White W. G. KRUMMRICH PLANT CHLOROPHENOL STUDY NUM3ER 115 115 106 113 2 RACE NUMBER 17 1 97 PERCENT 98.26 1.74 PERCENT 14.8 TABLE 2 STATUS OF EMPLOYEE-PARTICIPANT NUMBER ' PERCENT Active Hourly 89 77.4 Active Salary 23 . 20.0 By Contract 1 . .9 Not Working/Medical Reason 2 // ~ AGE 1.7 Age in Years NUMBER PERCENT 21 - 30 24 20.8 31 - 40 22 19.1 41-50 . 31 27.0 51 - 60 31 27.0 61 - 63 7 6.1 College Graduate Post - graduate 35 30.4 5 4.3 TABLE 3 OCCURRENCE OF CHLORACNE i Examined 106 History of Chloracne Current findings Severity mi 1d moderate * severe Type comedonal cystic pustular PERCENT NO YES POSITIVE 40 66 62.3 63 43 40.6 29 67.4 14 32.5 0 43 100.0 14 32.5 TABLE 4 DISTRIBUTION OF CHLORACNE # Examined 106 SKIN AREA Temporal Forehead Malar Cheeks * Occipital Neck Trunk Shoulders Genitalia 4 22 7 27 1 0 2 3 cP & TABLE 5 PRESENCE OF HIRSUTISM, ACTINIC ELASTOSIS AND CHLORACNE Hirsutism malar area Actinic Elastosis Severity mild moderate severe Area of Actinic Elastosis face neck Both Chloracne and Elastosis **r f"'1. PERCENT NO YES ? POSITF 101 5 4.7 94 12 11.3 6 50.0 4 ' 33.3 2 16.7 10 5 4 ^9.3 *** TABLE 6 OCCURRENCE OF ACNE VULGARIS NO YES History of * Current Acne Vulgaris 61 45 22 Severity mild 19 moderate 3 PERCENT 42.5 20.7 86.4 13.6 TABLE 7 Occurrence of Chloracne by Department Department 236 (pentaj Department 236 and 237 Department 237 (o and p chlorophenol) Total NO CHLORACNE 24 34 5 63 CHLORACNE 20 22 i (?j 43 S TABLE 8 RELATIONSHIP BETWEEN NUM8ER OF MONTHS IN PENTACHLOROPHENOL PRODUCTION AND DERMATOLOGIST HISTORY OF CHLORACNE NO HISTORY HISTORY OF CHLORACNE- 1 To 3 Mo. 31 4 To 5 Mo. 6 To II f-fo. 1 To 2 Yr. 13 10 16 11 n 2 Jo 3 Yr. 39 3 To 5 Yr. *, 3 8 5 To 10 Yr. 28 10 To 20 Yr. 17 undetermined 1 #237 only Total 5 40 co to PR 0 Among those workers in the survey the # of cases of chloracne is sig nificantly higher in those workers who have worked 2 or more years than in those who worked less than 2 years. 1 order* No History of chloracne History of chloracne LESS THAN 2 YR. 25 31 GREATER OR EQUAL TO 2 YR. 9 32 TABLE 9 RELATIONSHIP BETWEEN NUMBER MONTHS IN RENTACHLOROPHENOL PRODUCTION AND RESIDUAL CHLORACNE 1 To 3 Mo. 4 To 5vMo. 6 To 11 Mo. 1 To 2 Yr. 2 To 3 Yr. 3 To 5 Yr. 5 To 10 Yr. 10 To 20 Yr. undetermined #237 only NO RESIDUAL 3 3 15 14 6 6 6 3 2 5 63 RESIDUAL 1 1 11 8 6 5 4 5 1 i (?) gs* C O ^ 3' TABLE 10 RELATIONSHIP BETWEEN DUMBER OF MONTHS IN PENTACHLOROPHENOL PRODUCTION AND SEVERITY OF RESIDUAL CHLORACNE 1 To 3 Mo. 4 To 5 Mo. 6 To 11. Ho. 1 To 2 Yr. -2 To 3 Yr. 3 To 5 Yr. 5 To 10 Yr. ~-10 To 20 Yr. undetermined #237 only Total MILO 0 1 9 4 4 4 2 4 1 0 29 MODERATE 1 0 2 4 2 1 2 1 0 1 14 TABLE 11 RELATIONSHIP BETWEEN THE DATE OF LEAVING PENTACHLOROPHENOL PRODUCTION AND HISTORY OF CHLORACNE PERI00 1947 To 1952 1953 To 1958 1959 To 1964 1965 To 1970 1971 To 1976 1977 To 1979 undetermined only in #237 NO HISTORY 5 3 6 2 '8 10 1 5 s HISTORY 7 3 13 1 20 20 1 - 1. TABLE 12 RELATIONSHIP BETWEEN DATE OF LEAVING PENTACHLOROPHENOL PRODUCTION AND RESIDUAL CHLORACNE Period 1947 To 1952 1953 To 1958 1959 To 1954 1965 To 1970 1971 To 1976 1977 To 1979 undetermined Only in ?237 Total . No Residual 9 4 9 2 17 IS 2 5 63 Residual 3 2 10 1* 11 lb 0 1 43 TABLE 14 OTHER CLINICAL FINDINGS OCCURRENCE IN 106 PERSONS EXAMINED NUMBER PERCENT Folliculitis 10 9.4 Actinic Keratoses 3 2.8 Seborrheic Dermatitis 9 8.5 Dermatophytosis 35 33.0 Hands 1 Feet 31 Nails 6 Other 12 Atopic Dermatitis 1 .9 Poikiloderma Site Face Neck Chest Other TABLE 14 NUMBER Dermatofibroma 1 Lipoma 4 Pigmented Nevi 7 Rosacea/Rhi nophyma 5 Lichens Simplex Chronicus 3 Alopecia (other than pattern baldness) 0 Neurofibroma 0 Petechae of Ecchymoses 1 Depuytren *s Contract!*on 1 Junctional Nevi 1 Uymphadenopathy 2 PERCENT .9 3,8 6.6 4.7 2.8 .9 .9 .9 1.9 TABLE 14 Livido Reticularis (c. marmorata) Xerosis Pilonidal Cyst Oti tis .Externa Mild Chronic Dermatitis Xanthelasma Seborrheic Keratoses Psoriasis Squamous Cell Epithelioma Basal Cell Epithelioma . NUMBER 2 4 0 2 1 18 0 0 0 PERCENT I.9 3.8 1.9 .9 .9 7.5 c o ta g g ^ TABLE 15 Lipids, Total Serum Dermatologist History of Chi oracne Normal High undetermined Total NO HISTORY 39 1 40 HISTORY 64 1 1 66 WGK Lipids, Total Serum Chloracne Normal High Total Normal range 0.30 - 1.00 TABLE 16 Possible Relation Between Serum Triglycerides Dermatologist History of Chloracne Normal High NO HISTORY 32 8 HISTORY OF CHLORACNE 45 21 Possible Relation Between Triglycerides and Residual Chloracne Normal High NO RESIDUAL 51 12 RESIDUAL 26 17 Normal range 50.00 - 200.00 Triglycerides Severi Normal High Total 16 J_3 . 29 Normal range 50.00 - 200.00 MODERATE 10 4 14 TABLE 17 Relationship Between Serum Cholesterol and Dermatologist History of Chloracne NO HISTORY HISTORY OF CHLORACNE Normal 35 56 High 5 10 Total 40 66 WGK Normal High Total Cholesterol Residual Chloracne NO RESIDUAL * RESIDUAL 56 35 78 63 43 TABLE 18 LDL VS Dermatologist History of Chloracne Low Normal High undetermined Total NO HISTORY 0 29 11 40 HISTORY 1 48 16 1 66/ 'LDL vs RESIDUAL CHLORACNE Low Normal High undetermined Total NO RESIDUAL 0 47 RESIDUAL 1 30 .. Range mg/UL 60 - 185 TABLE 19 VLDL vs DERMATOLOGIST HISTORY OF CHLORACNE NO HISTORY Normal 36 High 4 undetermined Range mg/DL .00 - 40.0 HISTORY OF CHLORACNE 47 18 The incidence of high levels of VLDL is significantly greater in those having a history of chloracne than in those not having chloracne. (two-tail Fisher Exact Test, p=.049) TABLE 20 VLDL vs Residua] Chloracne Normal High undetermined NO RESIDUAL CHLORACNE 55 8 The incidence of high levels of VLDL is significantly higher in those having chloracne than is those not having chloracne. (two-tail Fisher Exact Test, p=.022) CHLORACNE 28 14 1 TABLE 21 Possible Relation Between G - Glutamyl Transpeptidase (GGT) and Dermatologist History of Chloracne Normal High undetermi ned Total NO HISTORY 36 4 40 HISTORY OF CHLORACNE 60 5 1 66 G - Glutamyl Transpeptidase (GGT) vs Residual Chloracne Normal High undetermined Total NO RESIDUAL 56 7 RESIDUAL CHLORACNE 40 .ft" Normal range units/L TABLE 22 Smoking vs Chloracne Smoke now Do not smoke never* smoked used to smoke Did not answer NO CHLORACNE 26 37 18 19 CHLORACNE 27 14 6 8 2 Significantly less chloracne was found in workers who do not smoke now (even if they smoked previously) than i n ^ workers who currently smoke. o r(two-tai 1 Fisher Exact Test, p=.02^> X'\JV "7 -> TABLE 23 DISTRIBUTION OF HDL AMONG PERSONS WITH NO HISTORY OF CHLORACNE, HISTORY OF CHLORACNE AND RESIDUAL CHLORACNE NO HISTORY L.T. 25 mg/DL 3 26-35 mg/DL 7 36-44 mg/DL 7 45-59 mg/DL 9 60-74 mg/DL 10 G.T. 75 ng/DL Total 4 40 HISTORY 8 14 14 15 12 2 65(+l) RESIDUAL 6 10 11 7 6 2 42+1) NO RESIDUAL 5 11 10 17 16 4' 63