Disclaimer: The information contained in these guidelines is intended for reference purposes only. It provides a summary of information about chemicals that workers may be exposed to in their workplaces. The information may be superseded by new developments in the field of industrial hygiene. Readers are therefore advised to regard these recomendations as general guidelines and to determine whether new information is available.

OCCUPATIONAL SAFETY AND HEALTH GUIDELINE FOR VINYL BROMIDE

INTRODUCTION

This guideline summarizes pertinent information about vinyl bromide for workers and employers as well as for physicians, industrial hygienists, and other occupational safety and health professionals who may need such information to conduct effective occupational safety and health programs. Recommendations may be superseded by new developments in these fields; readers are therefore advised to regard these recommendations as general guidelines and to determine whether new information is available.

SUBSTANCE IDENTIFICATION

* Formula

CH(2)CHBr

* Structure

(For Structure, see paper copy)

* Synonyms

Bromoethene; Bromoethylene; Monobromoethylene

* Identifiers

1. CAS No.: 593-60-2

2. RTECS No.: KU8400000

3. DOT UN: 1085 60 (vinyl bromide, inhibited)

4. DOT label: Flammable gas

* Appearance and odor

Vinyl bromide is a colorless, flammable gas with a pungent odor at standard pressure. Under pressure, this substance is a liquid.

CHEMICAL AND PHYSICAL PROPERTIES

* Physical data

1. Molecular weight: 106.96

2. Boiling point (at 760 mm Hg): 15.8 degrees C (60.4 degrees F)

3. Specific gravity (water = 1): 1.49 at 20 degrees C (68 degrees F)

4. Vapor density: 3.7

5. Melting point: þ139.5 degrees C (þ219.1 degrees F)

6. Vapor pressure at 20 degrees C (68 degrees F): 895 mm Hg

7. Solubility: Insoluble in water; soluble in alcohol, ether, acetone, benzene, or chloroform.

8. Evaporation rate: Data not available.

* Reactivity

1. Conditions contributing to instability: Polymerization may occur on contact of vinyl bromide with sunlight.

2. Incompatibilities: Contact of vinyl bromide with oxidizers (such as perchlorates, peroxides, perman-ganates, chlorates, and nitrates), heat, or open flame may cause violent reactions.

3. Hazardous decomposition products: Toxic gases (such as carbon monoxide, carbon dioxide, or bromine) may be released in a fire involving vinyl bromide.

4. Special precautions: None reported.

* Flammability

The National Fire Protection Association has assigned a flammability rating of 0 (no fire hazard) to vinyl bromide. However, other sources list vinyl bromide as a highly flammable gas.

1. Flash point: Vinyl bromide has no flash point by standard tests in air; however, with a high-energy ignition source it reaches explosive limits.

2. Autoignition temperature: 530 degrees C (986 degrees F)

3. Flammable limits in air (percent by volume): Lower, 9; upper, 15

4. Extinguishant: For small fires use dry chemical, carbon dioxide, water spray, or regular foam. For larger fires use water spray, fog, or regular foam.

EXPOSURE LIMITS

* OSHA PEL

The Occupational Safety and Health Administration (OSHA) does not currently regulate vinyl bromide.

* NIOSH REL

The National Institute for Occupational Safety and Health (NIOSH) considers vinyl bromide a potential human carcinogen and recommends that exposures be reduced to the lowest feasible concentration [NIOSH 1992].

* ACGIH TLV

The American Conference of Governmental Industrial Hygienists (ACGIH) has assigned vinyl bromide an A2 designation (suspected human carcinogen) and a threshold limit value (TLV) of 5 parts per million (ppm) parts of air (22 milligrams per cubic meter (mg/m(3))) as a TWA for a normal 8-hour workday and a 40-hour workweek [ACGIH 1994, p. 35].

* Rationale for Limits

The NIOSH limit is based on its potential to be an occupational carcinogen [NIOSH 1992].

The ACGIH limit is based on the risk of liver cancer [ACGIH 1991, p. 1691].

HEALTH HAZARD INFORMATION

* Routes of Exposure

Exposure to vinyl bromide can occur through inhalation and eye or skin contact.

* Summary of toxicology

1. Effects on Animals: Vinyl bromide causes central nervous system depression in animals at high levels and is carcinogenic in rats on chronic exposure. Liquid vinyl bromide is slightly to moderately irritating to rabbit eyes but is non-irritating to intact or abraded rabbit skin [ACGIH 1991; Hathaway et al. 1991]. The oral LD(50) in rats is 500 mg/kg [NIOSH 1991; ACGIH 1991]. Rats exposed to 100,000 ppm vinyl bromide died within 15 minutes, while those exposed to 50,000 ppm lost consciousness within 25 minutes and died after 7 hours of exposure (ACGIH 1991; Hathaway et al. 1991]. Slight to moderate kidney damage was seen at autopsy in rats surviving exposure to 50,000 ppm (ACGIH 1991; Clayton and Clayton 1981). Rats exposed to 25,000 ppm vinyl bromide were anesthetized but recovered rapidly even after 7 hours of exposure and showed no histopathological changes at autopsy [ACGIH 1991]. Male and female rats exposed to 10, 50, 250, or 1250 ppm vinyl bromide for 6 hours/day, 5 days/week for 104 weeks showed a dose-dependent increase in the incidence of liver angiosarcomas and Zymbal gland carcinomas. Increases were also observed in neoplastic nodules of the liver and in hepatocellular carcinomas [IARC, Vol. 39, 1986; ACGIH 1991]. Vinyl bromide was mutagenic to Salmonella typhimurium in the presence or absence of metabolic activation [IARC, Vol. 39, 1986]. Based on this evidence, IARC has concluded that the evidence for the carcinogenicity of vinyl bromide in animals is sufficient [IARC, Vol. 39, 1986].

2. Effects on Humans: The International Agency for Research on Cancer (IARC) concludes that there is no adequate data on the carcinogenicity of vinyl bromide in humans and classifies vinyl bromide as a Group 2A (probable human) carcinogen based on sufficient evidence of carcinogenicity in experimental animals [IARC, Suppl. 7, 1987].

* Signs and symptoms of exposure

1. Acute exposure: The signs and symptoms of acute exposure to vinyl bromide in humans may include irritation of the eyes. Acute exposure to high levels of vinyl bromide may cause dizziness and lightheadedness [NJDH 1986].

2. Chronic exposure: No signs or symptoms of chronic exposure to vinyl bromide have been reported in humans.

EMERGENCY MEDICAL PROCEDURES

* Emergency procedures [NIOSH to supply]

Rescue: Remove an incapacitated worker from further exposure and implement appropriate emergency procedures (e.g., those listed on the Material Safety Data Sheet required by OSHA's Hazard Communication Standard [29 CFR 1910.1200]). All workers should be familiar with emergency procedures, the location and proper use of emergency equipment, and methods of protecting themselves during rescue operations.

EXPOSURE SOURCES AND CONTROL METHODS

The following operations may involve vinyl bromide and lead to worker exposures to this substance:

• Production of flame-retardant synthetic fiber.
• Intermediate in organic synthesis.
• Preparation of plastics by polymerization or copolymerization.
• Manufacture and transportation of vinyl bromide.

Workers responding to a release or potential release of hazardous substances must be protected as required by paragraph (q) of OSHA's Hazardous Waste Operations and Emergency Response Standard [29 CFR 1910.120].

Methods that are effective in controlling worker exposures to vinyl bromide, depending on the feasibility of implementation, are as follows:

• Process enclosure
• Local exhaust ventilation
• General dilution ventilation
• Personal protective equipment

Good sources of information about control methods are as follows:

1. ACGIH [1992]. Industrial ventilation--a manual of recommended practice. 21st ed. Cincinnati, OH: American Conference of Governmental Industrial Hygienists.

2. Burton DJ [1986]. Industrial ventilation--a self study companion. Cincinnati, OH: American Conference of Governmental Industrial Hygienists.

3. Alden JL, Kane JM [1982]. Design of industrial ventilation systems. New York, NY: Industrial Press, Inc.

4. Wadden RA, Scheff PA [1987]. Engineering design for control of workplace hazards. New York, NY: McGraw-Hill.

5. Plog BA [1988]. Fundamentals of industrial hygiene. Chicago, IL: National Safety Council.

MEDICAL SURVEILLANCE

OSHA is currently developing requirements for the medical surveillance of workers. When these requirements have been promulgated, readers should refer to them for additional information and to determine whether employers whose employees are exposed to vinyl bromide are required to implement medical surveillance procedures.

Medical Screening:

Workers who may be exposed to chemical hazards should be monitored in a systematic program of medical surveillance that is intended to prevent occupational injury and disease. The program should include education of employers and workers about work-related hazards, early detection of adverse health effects, and referral of workers for diagnosis and treatment. The occurrence of disease or other work-related adverse health effects should prompt immediate evaluation of primary preventive measures (e.g., industrial hygiene monitoring, engineering controls, and personal protective equipment). A medical surveillance program is intended to supplement, not replace, such measures. To detect and control work-related health effects, medical evaluations should be performed (1) before job placement, (2) periodically during the term of employment, and (3) at the time of job transfer or termination.

* Preplacement medical evaluation

Before a worker is placed in a job with a potential for exposure to vinyl bromide, a licensed health care professional should evaluate and document the worker's baseline health status with thorough medical, environmental, and occupational histories, a physical examination, and physiologic and laboratory tests appropriate for the anticipated occupational risks. These should concentrate on the function and integrity of the liver and kidneys.

A preplacement medical evaluation is recommended to assess medical conditions that may be aggravated or may result in increased risk when a worker is exposed to vinyl bromide at or below the prescribed exposure limit. The health care professional should consider the probable frequency, intensity, and duration of exposure as well as the nature and degree of any applicable medical condition. Such conditions (which should not be regarded as absolute contraindications to job placement) include a history and other findings consistent with diseases of the liver and kidneys.

* Periodic medical evaluations

Occupational health interviews and physical examinations should be performed at regular intervals during the employment period, as mandated by any applicable Federal, State, or local standard. Where no standard exists and the hazard is minimal, evaluations should be conducted every 3 to 5 years or as frequently as recommended by an experienced occupational health physician. Additional examinations may be necessary if a worker develops symptoms attributable to vinyl bromide exposure. The interviews, examinations, and medical screening tests should focus on identifying the adverse effects of vinyl bromide on the liver and kidneys. Current health status should be compared with the baseline health status of the individual worker or with expected values for a suitable reference population.

* Termination medical evaluations

The medical, environmental, and occupational history interviews, the physical examination, and selected physiologic or laboratory tests that were conducted at the time of placement should be repeated at the time of job transfer or termination to determine the worker's medical status at the end of his or her employment. Any changes in the worker's health status should be compared with those expected for a suitable reference population. Because occupational exposure to vinyl bromide may cause diseases with prolonged latent periods, the need for medical surveillance may extend well beyond the termination of employment.

* Biological Monitoring

Biological monitoring involves sampling and analyzing body tissues or fluids to provide an index of exposure to a toxic substance or metabolite. No biological monitoring test acceptable for routine use has yet been developed for vinyl bromide.

WORKPLACE MONITORING AND MEASUREMENT

Determination of a worker's exposure to airborne vinyl bromide is made using a solid sorbent tube (coconut shell charcoal, 400 mg/200 mg). Samples are collected at a maximum flow rate of 0.2 liter/minute until a minimum collection volume of 10 liters is reached. The sample is then treated with 15 ml ethanol (30 minute ultrasonic agitation). Analysis is conducted by gas chromatography with flame ionization detector. This method is described in NIOSH Method No. 1009 [NIOSH 1994]. An alternative method can be used for the monitoring and analysis of vinyl bromide. Samples are collected on a coconut shell charcoal tube (100 mg/50mg). A maximum flow rate of 0.2 liter/minute is used to collect a maximum air volume of 5 liters. The samples are desorbed with carbon disulfide and analyzed by gas chromatography using a flame ionization detector. This method is described in OSHA Method #8. [CAUTION: When using OSHA Method #8, the samples must be refrigerated until analysis and analysis should be conducted as soon as possible].

PERSONAL HYGIENE PROCEDURES

If liquid vinyl bromide contacts the skin, workers should flush the affected areas immediately with plenty of water, followed by washing with soap and water.

Clothing contaminated with liquid vinyl bromide should be removed immediately, and provisions should be made for the safe removal of the chemical from the clothing.

A worker who handles liquid vinyl bromide should thoroughly wash hands, forearms, and face with soap and water before eating, using tobacco products, using toilet facilities, applying cosmetics, or taking medications.

Workers should not eat, drink, use tobacco products, apply cosmetics, or take medications in areas where vinyl bromide or a solution containing vinyl bromide is handled, processed, or stored.

STORAGE

Vinyl bromide should be stored in a cool, dry, well-ventilated area in tightly sealed containers that are labeled in accordance with OSHA's Hazard Communication Standard [29 CFR 1910.1200]. Containers of vinyl bromide should be protected from physical damage and should be stored separately from oxidizers (such as perchlorates, peroxides, permanganates, chlorates, and nitrates), heat, sparks, and open flame. Because containers that formerly contained vinyl bromide may still hold product residues, they should be handled appropriately.

SPILLS AND LEAKS

In the event of a spill or leak involving vinyl bromide, persons not wearing protective equipment and clothing should be restricted from contaminated areas until cleanup has been completed. The following steps should be undertaken following a spill or leak:

1. Do not touch or walk through the spilled material; stop the leak if it is possible to do so without risk.

2. For small liquid spills, take up with sand or other noncombustible absorbent material and place into closed containers for later disposal.

3. For large liquid spills, build dikes far ahead of the spill to contain the vinyl bromide for later reclamation or disposal.

SPECIAL REQUIREMENTS

U.S. Environmental Protection Agency (EPA) requirements for emergency planning, reportable quantities of hazardous releases, community right-to-know, and hazardous waste management may change over time. Users are therefore advised to determine periodically whether new information is available.

* Emergency planning requirements

Vinyl bromide is not subject to EPA emergency planning requirements under the Superfund Amendments and Reauthorization Act (SARA) (Title III) [42 USC 11022].

* Reportable quantity requirements for hazardous releases

Employers are not required by the emergency release notification provisions of the Comprehensive Environmental Response, Compensation, and Liability Act (CERCLA) [40 CFR Part 355.40] to notify the National Response Center of an accidental release of vinyl bromide; there is no reportable quantity for this substance.

* Community right-to-know requirements

Employers who own or operate facilities in SIC codes 20 to 39 that employ 10 or more workers and that manufacture 25,000 pounds or more of vinyl bromide per calendar year or otherwise use 10,000 pounds or more of vinyl bromide per calendar year are required by EPA [40 CFR Part 372.30] to submit a Toxic Chemical Release Inventory form (Form R) to EPA reporting the amount of vinyl bromide emitted or released from their facility annually.

* Hazardous waste management requirements

EPA considers a waste to be hazardous if it exhibits any of the following characteristics: ignitability, corrosivity, reactivity, or toxicity as defined in 40 CFR 261.21-261.24. Under the Resource Conservation and Recovery Act (RCRA) [40 USC 6901 et seq.], EPA has specifically listed many chemical wastes as hazardous. Although vinyl bromide is not specifically listed as a hazardous waste under RCRA, EPA requires employers to treat waste as hazardous if it exhibits any of the characteristics discussed above.

Providing detailed information about the removal and disposal of specific chemicals is beyond the scope of this guideline. The U.S. Department of Transportation, EPA, and State and local regulations should be followed to ensure that removal, transport, and disposal of this substance are conducted in accordance with existing regulations. To be certain that chemical waste disposal meets EPA regulatory requirements, employers should address any questions to the RCRA hotline at (202) 382-3000 (in Washington, D.C.) or toll-free at (800) 424-9346 (outside Washington, D.C.). In addition, relevant State and local authorities should be contacted for information on any requirements they may have for the waste removal and disposal of this substance.

RESPIRATORY PROTECTION

* Conditions for respirator use

Good industrial hygiene practice requires that engineering controls be used where feasible to reduce workplace concentrations of hazardous materials to the prescribed exposure limit. However, some situations may require the use of respirators to control exposure. Respirators must be worn if the ambient concentration of vinyl bromide exceeds prescribed exposure limits. Respirators may be used (1) before engineering controls have been installed, (2) during work operations such as maintenance or repair activities that involve unknown exposures, (3) during operations that require entry into tanks or closed vessels, and (4) during emergencies. Workers should only use respirators that have been approved by NIOSH and the Mine Safety and Health Administration (MSHA).

* Respiratory protection program

Employers should institute a complete respiratory protection program that, at a minimum, complies with the requirements of OSHA's Respiratory Protection Standard [29 CFR 1910.134]. Such a program must include respirator selection, an evaluation of the worker's ability to perform the work while wearing a respirator, the regular training of personnel, respirator fit testing, periodic workplace monitoring, and regular respirator maintenance, inspection, and cleaning. The implementation of an adequate respiratory protection program (including selection of the correct respirator) requires that a knowledgeable person be in charge of the program and that the program be evaluated regularly. For additional information on the selection and use of respirators and on the medical screening of respirator users, consult the latest edition of the NIOSH Respirator Decision Logic [NIOSH 1987b] and the NIOSH Guide to Industrial Respiratory Protection [NIOSH 1987a].

PERSONAL PROTECTIVE EQUIPMENT

Workers should use appropriate personal protective clothing and equipment that must be carefully selected, used, and maintained to be effective in preventing skin contact with vinyl bromide. The selection of the appropriate personal protective equipment (PPE) (e.g., gloves, sleeves, encapsulating suits) should be based on the extent of the worker's potential exposure to vinyl bromide.

To evaluate the use of personal protective equipment with vinyl bromide, users should consult the best available performance data and manufacturers recommendations. Significant differences have been demonstrated in the chemical resistance of generically similar PPE materials (e.g., butyl) produced by different manufacturers. In addition, the chemical resistance of a mixture may be significantly different from that of any of its neat components.

Any chemical-resistant clothing that is used should be periodically evaluated to determine its effectiveness in preventing dermal contact. Safety showers and eye wash stations should be located close to operations that involve vinyl bromide.

Splash-proof chemical safety goggles or face shields (20 to 30 cm long, minimum) should be worn during any operation in which a solvent, caustic, or the toxic substance may be splashed into the eyes.

In addition to the possible need for wearing protective outer apparel (e.g., aprons, encapsulating suits), workers should wear work uniforms, coveralls, or similar full-body coverings that are laundered each day. Employers should provide lockers or other closed areas to store work and street clothing separately. Employers should collect work clothing at the end of each work shift and provide for its laundering. Laundry personnel should be informed about the potential hazards of handling contaminated clothing and instructed about measures to minimize their health risk.

Protective clothing should be kept free of oil and grease and should be inspected and maintained regularly to preserve its effectiveness.

Protective clothing may interfere with the body's heat dissipation, especially during hot weather or during work in hot or poorly ventilated work environments.

REFERENCES

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