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1 VINYL CHLORIDE SAFETY HAZARDS
Vinyl chloride, a gas at atmospheric temperatures and pressures, is made from ethylene and chlorine by any one of several processes. As a liquid it boils at 7F. As a gas it has a sweet, pleasant odor that can usually be detected at 0. 2% or 2, 000 ppm in air. Vinyl chloride is reacted with itself or other monomers such as vinyl acetate or acrylonitrile to make synthetic resins such as polyvinyl chloride, or polyvinyl chloride containing resins such as Dynel resin or Solvent resins.
The safety hazards related to vinyl chloride are as follows: 1. Flammability 2. Reactivity 3. Short-Term Toxicity 4. Long-Term Toxicity
Vinyl chloride, when mixed with air, yields a flammable mixture. The flammable concentration in air ranges from a lower limit of 3. 6% to an upper 1 limit of 26.4%. The gas, vinyl chloride, is twice as heavy as air; therefore, it tends to collect in low spots unless there is wind blowing or good ventilation. Ton gallons of liquid vinyl chloride spilled on the ground creates a flammable gas cloud about 19 feet in diameter.
The reactivity of vinyl chloride is the property that makes it a useful chemical as well as contributing to its hazard. In the presence of a peroxide catalyst, vinyl chloride will react with itself or other monomers to form a
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2. solid material and will release heat. The solid, or polyvinyl chloride as it is called, is not flammable or hazardous; the heat is, however.. If the heat released by the reaction is not promptly removed by cooling or by relief valves, the reactor or tank containing the vinyl chloride will be over-pressured and may explode violently. Vinyl chloride will also react with oxygen in air to form polyperoxides which are solids that can explode or catch fire'spontaneously.
The toxicity or effect of vinyl chloride on man has been under study by industry for many years. At first, it was considered relatively harmless but, as more became known, there are indications that some definite hazards exist.
The hazards that result from short-term exposure are fairly wellknown; these are as follows:
1. Short-term exposure to concentrations of vinyl chloride in air of 8% (80,000 ppm) or more can cause unconsciousness and even death.
2. Short-term exposure to concentrations of vinyl chloride in air of 1.6% (16,000 ppm) or more will cause drunkenness or loss of coordination.
3. Short-term exposure to concentrations of vinyl chloride in air of 0. 6% (6, 000 ppm) will cause lightheadedness or wooziness.
In general, when a person is exposed to these concentrations and he is removed from exposure, the conditions of unconsciousness or drunkenness clear up quickly.
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3. The hazards resulting from exposure to vinyl chloride over a long period of time (years) are not so clearly defined. Long-term exposure to vinyl chloride is suspected to cause acroosteolysis- a deterioration of the bones particularly in the fingers, and angiosarcoma - a cancer of the blood vessel walls usually in the liver.
Acroosteolysis was first identified in the United States in 1967 by B. F. Goodrich of Louisville, Kentucky. Acroosteolysis is a disease characterized by loss of calcium in the finger bones, a shortening of the fingers, and a tendency for the hands to blanch on exposure to cold. An industry-wide study by Manufacturing Chemists Association failed to identify the cause; how ever, exposure to vinyl chloride was suspect. Reductions were made in vinyl chloride exposure, particularly in autoclave cleaning, and no new cases of acro osteolysis have been found since.
Angiosarcoma in vinyl chloride workers was first reported in January of 1974 by B. F. Goodrich at Louisville, Kentucky. This relatively rare form of cancer was known to be caused by exposure to arsenical materials and by the use of a thorium compound in liver X-rays. Prior to the Goodrich report, industry-sponsored laboratory studies were in progress in Italy under Dr. Cesare Maltoni, and in Chicago at Industrial Bio-Test Laboratory. Preliminary results from these long-term exposure studies of rats, mice, and hamsters showed that vinyl chloride exposures as low as 50 ppm for half an animal's lifetime caused angiosarcoma and other tumors in all three species. An industry-wide study showed cases of human angiosarcoma at B, F. Goodrich's
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Louisville, Kentucky plant, at Goodyear's Niagara Falls plant, at
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Union Carbide's South Charleston, West Virginia plant, and at Firestone's
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Pottstown, Pennsylvania pla-nt. All in all, fifteen clear cases were identified
as occurring since 1961 in 6, 000 workers. No human cases of angiosarcoma
have been found where exposures to vinyl chloride were 100 ppm or less. Because
there are fifteen cases of angiosarcoma in workers exposed.to vinyl chloride
and three species of animals developed angiosarcoma and other tumors when
exposed to vinyl chloride for long periods, the OSHA of the Department of Labor
has declared that vinyl chloride is a carcinogen and that exposures to vinyl
chloride must be limited to an average 1 ppm over an eight-hour period, and
has established an OSHA standard controlling exposure to vinyl chloride.
To summarize the known facts regarding angiosarcoma:
1. Angiosarcoma has been induced in rats and mice by long-term exposure to 50 ppm of vinyl chloride.
2. Angiosarcoma appeared in vinyl chloride workers at the B. F. Goodrich Louisville plant more often than it appeared in a normal population.
3. There is no evidence that concentrations of 50 ppm or less cause angiosarcoma in humans.
4. There is no evidence that polyvinyl chloride is harmful to anyone.
RN Wheeler Jr/ra December 2, 1974
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DEPARTMENT OF LABOR "OSHA" STANDARD
ON EXPOSURE TO VINYL CHLORIDE, EFFECTIVE JANUARY 1, 1975
Employee Handout
The Standard applies to all employees who are engaged in the production, packaging, storage, handling, or use of vinyl chloride or vinyl chloride resins and to support personnel (ie., maintenance employees who may be exposed to vinyl chloride areas)*
Vinyl chloride Is a gas at ordinary temperatures and pressures.
The OSHA Standard states that employees may not breathe VCl concentrations in air greater than:
1. 1.0 ppm averaged over any 8-hour period.
2. 5.0 ppm averaged over any 15-minute period except that-the calendar year 1975, the employee has an option regarding the wearing of respiratory.equipmont when VCM levels are below 25 ppm.
In addition, no employee may be exposed to direct contact with liquid vinyl chloride.
A program of monitoring or measurement of vinyl chloride concentrations in the breathing air of each establishment shall be undertaken to determine the exposure of employees.
Employees or their designated representatives may be given reasonable opportunity to observe the monitoring or measuring and to see documented results.
An employee exposed to vinyl chloride concentrations in his work space air in excess of the permissible limits shall be notified of this fact in writing within 10 days.
Busic Actions Required for Compliance
1. Opjtating Equipment and Job Procedures may not be changed in such a way that employees are exposed to concentrations of vinyl chloride in excess of the p rmissible limits.
2. Training will be given to employees who either work with or are exposed to vinyl chloride or vinyl chloride resin.
3. A Medical Surveillance Program will be initiated for each employee exposed to vinyl chloride.
4. Medical, Monitoring and Work History Records will be maintained at least 30 years.
Additional Compliance Actions Required When Vinyl Chloride Exposure Exceeds the Standard
Operating equipment and procedures shall immediately be used to reduce exposures to the permissible limits. Where this is not adequate to reduce exposures to the permissible
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limits, (hoy shall nevertheless be used to reduce exposures to the lowest practicable level and employees shall use respiratory equipment. In addition, a plan or program shall be established and implemented to reduce exposures to the permissible limits solely by changes in cquipmont and operating procedures as socn as possible. This plan is to be updated every six months. During the year 1975, an employee may choose not to wear respiratory pro tection if the vinyl chloride concentration in air is 25 ppm or less.
A regulated area is to be established where vinyl chloride or polyvinyl chloride is manufactured, reacted, packaged, stored, handled, or used and the vinyl chloride conccntiation in the breathing air exceeds the permissible limit. A regulated area 5s an area containing one or more hazardous operations done on a more or less permanent basis.
Critical features of a regulated area are:
a. Access to the regulated area is limited to authorized personnel.
b. Entrances to regulated areas must be posted with signs bearing the legend:
Cancer-Suspect Agent Area Authorized Personnel Only
c. A daily roster or list of persons entering the regulated area shall be kept permanently.
Written operational plans for each emergency situation shall be developed where equip ment failure, etc., results in a massive release of VCM. These plans shall provide that employees engaged in hazardous operations shall be protected via respiratory equipment and all other employees not so protected shall evacuate the area until conditions are controlled and the emergency abated.
Reports are to be made as follows:
Regulated areas shall be registered with the OSHA Area Director within one month of their establishment.
Emergencies, with appropriate available facts, shall be reported within 24 hours to the OSHA Area Director. The Area Director may request that a full report, in writing, be made later.
An employee shall be notified, in writing, within 10 days following any monitoring or measuring which discloses that he has been exposed to vinyl chloride concentiutions in excess of the permissible limits without regard to the use of res piratory protection. He will also be apprised of the steps to be taken to prevent future exposures in excess of the permissible limits.
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