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Fluoride Dusts and Fumes in AEC Workplaces
 
Excerpt from:

Public Relations Problems in Connection with Occupational Diseases in the Beryllium Industry

Robert Tumbleson, 1947

United States Atomic Energy Commission
Public & Technical Information Service

(See scanned photocopy of this document)

In December 1946, members of the Industrial Hygiene Section, Rochester Atomic Energy Project, surveyed hazardous areas of the plant to determine atmospheric dust and fume concentrations and particle size. Air-dust samples were taken at three locations: the beryllium metal furnace, the beryllium fluoride furnace and the rotary kiln drier used in ore treatment. During pouring operations at the metal furnace samples taken by three different methods showed a range of beryllium concentrations varying from 0.29 to 4.71 mg/m3. During the coke-removal period at the same location the concentration decreased, with samples varying from 0.06 to 0.53 mg/m3. One sample taken during the pouring phase in a position over the top of the furnace analyzed 1.55 mg/m3 fluorine. All particle-size mass distributions obtained within this area showed atypical form of distribution indicating a mixture of dust and fume arises, with a mass median value of 0.8 [illegible].

Samples taken during the pouring phase at the beryllium fluoride furnace analyzed from 0.002 to 0.070 mg/m3 beryllium and 2.29 to 64.1 mg/m3 fluoride. One sample taken immediately after pouring analyzed 0.32 mg/m3 fluorine. Both particle size mass distributions obtained during the pouring were normal with median of 2.46 micron and a geometric standard deviation of 2.26 micron. The sample taken immediately after pouring showed fluorine present in extremely small sizes, the mass median size being below 0.1 micron.

The authors conclude that the relatively high fluoride concentrations obtained in the surveyed areas are of particular significance since they may represent a hazard by themselves and also suggest a combined action with beryllium. Further study of this factor is suggested, especially near the beryllium fluoride furnace where the relative fluoride concentration was 1000 times that of beryllium.

A pre-employment medical examination is given by the plant physician, who considers vital capacity, chest x-ray and previous history of respiratory diseases and allergies as major items of interest. The skin is also examined under ultraviolet light by means of a Burdette unit. A weekly vital capacity test is made on all plant employees during their employment, and chest x-rays are taken on all workers at 6-month intervals. Employees are encouraged to report to the plant physician at the first sign of dermatologic or respiratory trouble and employees suspected of being ill are placed immediately on a so-called prophylactic lay-off (PLC) which may extend up to two weeks. The PLC is conducted and paid for by the company and has no connection with the occupational disease (OC) program of the Ohio Compensation Commission. Under PLO workers receive 80% of their base wage. The company pays $1.32 (1.01 accident - 0.31 occupational disease) per $100 payroll to the Ohio Compensation Commission. This rate is partially based on the previous experience of the plant, and compares with a rate of $1.40 per $100 (1.10 accident - 0.30 occupational disease) for all chemical companies.

All employees are routinely given daily capsules of Benadryl (beta-dimethylaminoethyl benahydryl ether hydrochloride). The plant physician is convinced that this treatment, which was started about 4 months ago, has reduced the frequency and severity of dermatitis attacks.

The plant physician prepares a weekly health report which is always included on the agenda of the weekly management meeting.

During the year 1946 the Beryllium Corporation, Reading, Pa., employed a total of about 400 employees; but of these only about 100 were working in parts of the plant processing beryllium oxide or beryllium metal from the ore. During this same year a total of 557 workdays were lost "due to dust and fumes". Of these 20 days were attributed to dermatitis, while 537 lost workdays were charged to respiratory diseases. Seven cases were diagnosed as "industrial pneumonitis" and 7 were given miscellaneous diagnoses involving the respiratory system. No breakdown is available showing the sections of the plant in which these cases occurred. On the average each case of respiratory infection represented about 38 lost work days.

During the months October-December 1945, the Bureau of Industrial Hygiene, Pennsylvania Department of Health, made a study of the health hazards in this plant. Absenteeism was relatively high, the daily rate averaging about 6. Employment turnover was in the neighborhood of 100 per year. For the month of September 1943, 36 lost time cases reported to the plant physician for treatment. Of these 14 persons (39%) were treated for dermatitis, 9 persons (26%) for chest involvement, and the remaining 13 (36%) for injuries incurred through accidents at work. A total of 529 workers were employed in the plant in actual production during this period, so that the monthly attact rates were 26.4 and 17.1 per 1000 for dermatitis and respiratory diseases respectively.

While recognizing the abnormally high rates existing in this plant, both the company officials and representatives of the state health department attributed them not to beryllium per se but to the presence of fluorides in the plant. (Note: Following the Saranac Symposium the plant physician told the write that he had changed his mind in this connection. On the opening day, howerver, Mr. H.C. Kaweski, Metallurgist for the plant tended to minimize the effect of beryllium as an occupational hazard.) Thirty-seven atmospheric fluoride samples were collected and analyzed for fluorine, which averaged 0.450 mg/m3 of air. Four samples were taken for dust concentration determination. In the foundry the dust concentration averaged 4.62 * 10 6 particles/ ft3 of air, and the general atmosphere during cleaning of the crucible furnaces averaged 3.18 * 10 6 particles/ft3. The average dust particle size for 6 samples was very small, with all particles less than 1.17 microns and many less than 0.1 micron. In conclusion the investigators stated that to reduce absenteeism and to prevent sickness, respiratory ailments and dermatitis, the concentration of fluorine should be reduced to 0.09 mg/m3, or less. No analyses for beryllium dusts were made.


Quote of Note: "...beryllium is of itself not toxic... it appears that whatever toxicity has been found to occur with the beryllium salts is due to the toxicity of the acid radical such as the fluoride or oxyfluoride..." Hyslop et al., - NIH Public Health Service Bulletin No. 181 (1943).


The following declassified study was perfomed under "Contract W-7401-eng-49 for the Manhattan Project at the University of Rochester at the suggestion of Harold C. Hodge, professor of pharmacology and toxicology" (JADA).

The study was later published in an edited and altered form, in the Journal of the American Dental Association, August 1948, Vol. 27, No. 2, p 131-140.

A STUDY OF DENTAL CONDITIONS IN WORKERS EXPOSED TO DILUTE AND ANHYDROUS HYDROFLUORIC ACID IN PRODUCTIONS

PRELIMINARY REPORT OF ORAL EXAMINATIONS OF FORTY-SEVEN WORKERS AT THE CLEVELAND PLANT OF THE HARSHAW CHEMICAL COMPANY

Cleveland, Ohio, October 13-14-15, 1943

Of the forty-seven men examined, thirty-six were actively engaged in the production of hydrofluoric acid and were working continuously in an atmosphere laden with acid fumes. Eleven were employed in the plant offices or in sections of the plant removed from direct contact with hydrofluoric acid or its fumes. No women were accepted for study.

Findings

The hydrofluoric acid workers examined, on the whole, appeared to be unusually healthy men, physically sound, and comparatively immune to colds, infections and other commonplace illnesses. Active carious lesions were not observed in subjects exposed to the acid in production. This finding was made in spite of the fact that, as a group, these men neglected their mouths, employed little or no oral hygiene, and were in large proportion edentulous or nearly edentulous. Periodontoclasia was a common finding in subjects of experimental and control groups, but it is not likely that the incidence and severity of the disease was greater than in other men of comparable age and living habits.

The teeth of the men exposed to the acid appeared to be either highly polished and glasslike, presenting a surface comparable to that of highly glazed porcelain, or dulled with a peculiar brownish deposit which seemed to cover the enamel of the anterior teeth in especially large quantity. Although visual examination did not ascertain whether the teeth suffered loss of substance as a result of the action of the acid, there was some indication that there may have been etched and polished by it. In this connection, it may be of interest to note that the teeth of exposed individuals revealed more than the usual signs of attrition, and that although most of the men chewed tobacco to preven inhalation of dust and fumes, it is possible that exposure of the teeth to the influence of acid may have contributed to the attrition observed.

Environment

The concentration of obnoxious dust and fumes in the atmosphere of the production plant discouraged the presence of domestic animals such as the dog or cat. It was found through conversation with the men that fruit allowed to stand in th atmosphere of the plant would dehydrate but not rot. Bacterial cultures of organisms collected from the air adjacent to and remote from the scene of acid production indicated fewer organisms exist in the presence of the fumes. It is not unreasonable to postulate that this finding may be related to the comparatively high degree of immunity to colds, and infection enjoyed by the plant workers.

Further evidence of air pollution was found in the observation that window glass in buildings housing retorts became corroded in a few months time. The destruction was of such a magnitude as to require frequent periodic replacement of the glass in the windows of several buildings. It was noted, also, that men wearing spectacles, who work in the acid atmosphere, were continually required to renew the lenses of their eyepieces.

A few workers engaged near anhydrous acid retorts were seen with a condition of hyperemia of the skin of the face, transitory in nature, and due ostensibly to exposure to momentarily higher-than-usual concentrations of hydrofluoric acid in the air. Despite precautions against exposure, the skin of the face and hands of the acid workers as a whole was notably dehydrated, roughened, and irritated. Variation in the susceptibility of different individuals to the irritating influence of the acid was encountered by the Company, it being found that most fair-complexioned men could not be employed in the production plant.

Miscellany

Ulcerous lesions, chiefly on the hands and forearms, were observed in men who had accidentally been splashed by the acid. Protection of the feet was accomplished by the employment of rubber boots. This measure was instituted when it was found that ordinary leather shoes would disintegrate as a result of the action of the acid, particularly on the shoe nails.

Milk was an important ingredient of the diets of a large majority of the acid workers. Several veterans of the production plant expressed the opinion that they felt better and worked more efficiently with a "full stomach" containing plenty of that dairy product.

Since large quantities of vitriol are employed in the production of hydrofluoric acid, it may be possible that some of the effects described are attributable to the influence of sulphuric acid.

Recommendations

An analysis of the observations suggests certain procedures and tests designed to extend the study begun by the examinations:

1. A Iactobacillus study of exposed and unexposed individuals.

2. Urinalysis for fluoride in both groups.

3. A photographis study of superficial and ulcerous lesions caused by acid exposure.

4. Analysis of the dental plaque material found on the teeth of exposed workers.

5. Gross and microscopic studies of dental tissues from exposed and unexposed persons.

6. Studies of the effects of dilute and anhydrous hydrofluoric acid on the teeth of men (in vitro) and dogs (in vivo). These experiments should be planned to yield data regarding solubility and physical changes.

Signed

Peter P. Dale
Dental Pathologist

H. Berton McCauley
Dental Consultant

 

 

 

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