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 The information may be superseded by new developments in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 VINYLIDENE CHLORIDE
INTRODUCTION
This guideline summarizes pertinent information about vinylidene
chloride 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superseded by new developments in these fields; readers are therefore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
C(2)H(2)Cl(2)
* Structure
(For Structure, see paper copy)
* Synonyms
1,1-Dichloroethene; 1,1-dichloroethylene; sconatex; vinylidine
chloride; vinylidene dichloride; VDC
* Identifiers
1. CAS No.: 75-35-4
2. RTECS No.: KV9275000
3. DOT UN: 1303 26
4. DOT label: Flammable liquid
* Appearance and odor
Vinylidene chloride is a colorless liquid with a mild, sweet,
chloroform-like odor. Odor thresholds ranging from 190 to 500 parts
per million (ppm) parts of air have been reported.
CHEMICAL AND PHYSICAL PROPERTIES
* Physical data
1. Molecular weight: 96.94
2. Boiling point (at 760 mm Hg): 31.7 degrees C (89.1 degrees F)
3. Specific gravity: 1.21 at 20 degrees C (68 degrees F)
4. Vapor density: 3.4
5. Melting point: -122.5 degrees C (-188.5 degrees F)
6. Vapor pressure at 25 degrees C (77 degrees F): 591 mm Hg
7. Solubility: Practically insoluble in water; soluble in most
organic solvents.
8. Evaporation rate: Data not available.
* Reactivity
1. Conditions contributing to instability: Vinylidene chloride is
a self-reactive material. If stored at temperatures between
-40 degrees C (-40 degrees F) and 25 degrees C (77 degrees F) in
air without an inhibitor, it will absorb oxygen and form a
violently explosive peroxide.
2. Incompatibilities: Contact between vinylidene chloride and
aluminum, sunlight, copper, oxidizers, chlorosulfonic acid,
nitric acid, or oleum should be avoided to prevent violent
reactions.
3. Hazardous decomposition products: Toxic gases such as chlorine,
hydrogen chloride, phosgene, and formaldehyde may be released in
a fire involving vinylidene chloride.
4. Special precautions: Store in tanks with nickel, glass, or
baked phenolic linings at -10 degrees C (14 degrees F) and away
from all polymerization initiators or under a nitrogen blanket.
* Flammability
The National Fire Protection Association has assigned a
flammability rating of 4 (severe fire hazard) to vinylidene
chloride.
1. Flash point: -28 degrees C (-19 degrees F) (closed cup)
2. Autoignition temperature: 570 degrees C (1058 degrees F)
3. Flammable limits in air (percent by volume): Lower, 5.6; upper,
11.4
4. Extinguishant: For small fires use dry chemical, carbon dioxide,
water spray or alcohol-resistant foam. Use water spray, fog, or
alcohol-resistant foam to fight large fires involving vinylidene
chloride.
Fires involving vinylidene chloride should be fought upwind from
the maximum distance possible. Keep unnecessary people away;
isolate the hazard area and deny entry. Isolate the area for
1/2 mile in all directions if a tank, rail car, or tank truck is
involved in the fire. For a massive fire in a cargo area, use
unmanned hose holders or monitor nozzles; if this is impossible,
withdraw from the area and let the fire burn. Emergency
personnel should stay out of low areas. Vapors may travel to a
source of ignition and flash back. Vapors are an explosion and
poison hazard indoors, outdoors, or in sewers. Containers of
vinylidene chloride may explode in the heat of the fire and
should be moved from the fire area if it is possible to do so
safely. If this is not possible, cool fire exposed containers
from the sides with water until well after the fire is out. Stay
away from the ends of containers. Personnel should withdraw
immediately if a rising sound from a venting safety device is
heard or if there is discoloration of a container due to fire.
Firefighters should wear a full set of protective clothing and
self-contained breathing apparatus when fighting fires involving
vinylidene chloride.
EXPOSURE LIMITS
* OSHA PEL
The Occupational Safety and Health Administration (OSHA) does
not currently regulate vinylidene chloride.
* NIOSH REL
The National Institute for Occupational Safety and Health
(NIOSH) has established a recommended exposure limit (REL) for
vinylidene chloride of the lowest feasible concentration (0.4
ppm, limit of quantitation). NIOSH also considers vinylidene
chloride to be a potential human carcinogen [NIOSH 1992].
* ACGIH TLV
The American Conference of Governmental Industrial Hygienists
(ACGIH) has assigned vinylidene chloride a threshold limit value
(TLV) of 5 ppm (20 mg/m(3)) as a TWA for a normal 8-hour workday
and a 40-hour workweek and a short-term exposure limit (STEL) of
20 ppm (79 mg/m(3)) for periods not to exceed 15 minutes.
Exposures at the STEL concentration should not be repeated more
than four times a day and should be separated by intervals of at
least 60 minutes [ACGIH 1994, p. 36].
* Rationale for Limits
The NIOSH limit is based on the risk of potential cancer (liver
and kidney tumors in animals) [NIOSH 1992].
The ACGIH limits are based on the risk of renal, hepatic, or
other systemic toxicity [ACGIH 1991, p. 1714].
HEALTH HAZARD INFORMATION
* Routes of Exposure
Exposure to vinylidene chloride can occur through inhalation,
ingestion, and eye or skin contact.
* Summary of toxicology
1. Effects on Animals: Vinylidene chloride is hepatotoxic,
nephrotoxic, and mutagenic in experimental animals. In
addition, it can affect the developing embryo and there is
limited evidence of carcinogenic activity in experimental
animals. Liquid vinylidene chloride causes transient eye
irritation, but there is little effect on the skin if it is
allowed to evaporate [ACGIH 1991]. The acute toxicity of
vinylidene chloride is dependent on the state of the experimental
animals [IARC 1986]. Its toxicity is higher in fasted animals
than in fed animals, and the hepatic glutathione levels in the
animals can affect the toxicity of vinylidene chloride. The
oral LD(50) in rats is 200 mg/kg [NIOSH 1991]. The 4-hour
LC(50) in rats is 6,350 ppm [NIOSH 1991]. In a six month
inhalation study, rats, rabbits, guinea pigs, and dogs were
exposed to vinylidene chloride concentrations of 25, 50, or 100
ppm for 8 hours/day, 5 days/week [Clayton and Clayton 1981;
ACGIH 1991]. Signs of hepatic and renal degeneration were
observed at all doses. In a three generation reproductive
toxicity study, rats were administered vinylidene chloride at
concentrations of 0, 50, 100, or 200 ppm in their drinking water
[ACGIH 1991]. Although mild dose related hepatotoxicity was
observed, no alterations in fertility, body weight or clinical
signs could be detected. In a teratogenicity study, rats and
rabbits were exposed by inhalation to 10, 80 or 160 ppm
vinylidene chloride for 7 hours/day on gestation days 6 to 15
(rats) or 6 to 18 (rabbits) [ACGIH 1991; IARC 1986]. Increased
resorptions were observed in rabbits exposed to 160 ppm, while
increased incidences of skeletal malformations were observed in
rats exposed to 80 and 160 ppm and rabbits exposed to 160 ppm.
These exposures were toxic to the dams [ACGIH 1991; IARC 1986].
Vinylidene chloride was mutagenic in bacterial assays in the
presence of metabolic activation; it also caused DNA damage in
in vitro or in vivo assays. However, vinylidene chloride did not
cause mutations in mammalian cells or chromosomal effects in in
vitro or in vivo assays [ACGIH 1991; IARC 1986]. Vinylidene
chloride was tested for carcinogenicity in mice and rats by oral
administration and inhalation exposure, in mice by topical
exposure, and in hamsters by inhalation [IARC 1986]. Studies in
mice and rats by oral administration gave negative results. The
inhalation studies resulted in no treatment-related neoplasms in
either the rats or hamsters; in mice, the treatment related
increases in the incidence of kidney adenocarcinomas were
observed as were increases in mammary carcinomas in females and
pulmonary adenomas in both male and female mice. In
skin-painting studies conducted on female mice, vinylidene chloride
showed activity as an initiator, but in a study of repeated skin
application, no skin tumors occurred [IARC 1986]. IARC concluded
that there is limited evidence for the carcinogenicity of
vinylidene chloride to experimental animals [IARC 1986].
2. Effects on Humans: Vinylidene chloride is an eye irritant and
can affect the central nervous system, liver, and kidneys in
humans. Contact with the eyes can cause conjunctivitis and
transient corneal injury [IARC 1986]. Workers exposed to high
concentrations (4,000 ppm) of vinylidene chloride may show signs
of central nervous system depression with accompanying signs of
intoxication that may progress to unconsciousness [ACGIH 1991].
Repeated exposures to low concentrations are associated with
liver and kidney dysfunction [NLM 1992]. IARC concluded that in
the absence of adequate epidemiologic data, no evaluation of the
carcinogenicity of vinylidene chloride to humans could be made
[IARC 1986].
* Signs and symptoms of exposure
1. Acute exposure: Acute exposures to high concentrations of
vinylidene chloride may cause eye irritation and the signs and
symptoms characteristic to central nervous system depression
including drowsiness, nausea, headache, unsteadiness, or
unconsciousness.
2. Chronic exposure: No signs or symptoms of chronic exposure to
vinylidene chloride have been reported in humans. However,
chronic exposure may lead to liver or kidney damage and the
signs and symptoms of such damage may be apparent.
EMERGENCY MEDICAL PROCEDURES
* Emergency medical procedures: [NIOSH to supply]
5. 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 vinylidene chloride and lead to
worker exposures to this substance:
- The manufacture and transportation of vinylidene chloride
- Use in the production of copolymers with vinyl chloride or
acrylonitrile
- Use in the production of 1,1,1-trichloroethane, refrigerant
142b, and other chemicals
- Use in latexes, polymer lacquers, binders, and in fiber
production
Methods that are effective in controlling worker exposures to
vinylidene chloride, depending on the feasibility of
implementation, are as follows:
- Process enclosure
- Local exhaust ventilation
- General dilution ventilation
- Personal protective equipment
Workers responding to a release or potential release of a
hazardous substance must be protected as required by paragraph
(q) of OSHA's Hazardous Waste Operations and Emergency Response
Standard [29 CFR 1910.120].
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 medical surveillance.
When these requirements are promulgated, readers should refer to them
for additional information and to determine whether employers whose
employees are exposed to vinylidene chloride 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 vinylidene chloride, 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 vinylidene chloride
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 or 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 vinylidene chloride exposure. The
interviews, examinations, and medical screening tests should
focus on identifying the adverse effects of vinylidene chloride
on the liver or 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.
* 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 vinylidene
chloride.
WORKPLACE MONITORING AND MEASUREMENT
Determination of a worker's exposure to airborne vinylidene chloride
is made using a charcoal tube (100/50 mg sections, 20/40 mesh).
Samples are collected at a maximum flow rate of 0.2 liter/minute
until a maximum collection volume of 3 liters is reached. The sample
is then treated with carbon disulfide. Analysis is conducted by gas
chromatography using a flame ionization detector (GC/FID). This
method (OSHA 19) is described in the OSHA Computerized Information
System [OSHA 1994] and is fully validated. NIOSH has published a
similar method (Method No. 1015) for the sampling and analysis of
vinylidene chloride [NIOSH 1994b].
PERSONAL HYGIENE PROCEDURES
If vinylidene chloride contacts the skin, workers should immediately
wash the affected areas with large amounts of soap and water.
Clothing contaminated with vinylidene chloride should be removed
immediately, and provisions should be made for the safe removal of
the chemical from the clothing. Persons laundering the clothes
should be informed of the hazardous properties of vinylidene
chloride.
A worker who handles vinylidene chloride should thoroughly wash
hands, forearms, and face with soap and water before eating, using
tobacco products, using toilet facilities, applying cosmetics, or
taking medication.
Workers should not eat, drink, use tobacco products, apply cosmetics,
or take medication in areas where vinylidene chloride or a solution
containing vinylidene chloride is handled, processed, or stored.
STORAGE
Vinylidene chloride 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]. Store in
tanks with nickel, glass, or baked phenolic linings at -10 degrees C
(14 degrees F) and away from all polymerization initiators or under a
nitrogen blanket. Containers of vinylidene chloride should be
protected from physical damage and sunlight, and should be stored
separately from aluminum, copper, oxidizers, chlorosulfonic acid,
nitric acid, or oleum.
SPILLS AND LEAKS
In the event of a spill or leak involving vinylidene chloride,
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 the spilled material; stop the leak if it is
possible to do so without risk.
2. Notify safety personnel.
3. Remove all sources of heat and ignition.
4. Ventilate the area of the spill or leak.
5. Water spray may be used to reduce vapors, but the spray may not
prevent ignition in closed spaces.
6. For small spills, take up with sand or other noncombustible
absorbent material and place into closed containers for later
disposal.
7. For large liquid spills, build dikes far ahead of the spill to
contain the vinylidene chloride 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
Vinylidene chloride is not subject to EPA emergency planning
requirements under the Superfund Amendments and Reauthorization
Act (SARA) (Title III) in 42 USC 11022.
* Reportable quantity requirements for hazardous releases
A hazardous substance release is defined by EPA as any spilling,
leaking, pumping, pouring, emitting, emptying, discharging,
injecting, escaping, leaching, dumping, or disposing into the
environment (including the abandonment or discarding of
contaminated containers) of hazardous substances. In the event
of a release that is above the reportable quantity for that
chemical, employers are required to notify the proper Federal,
State, and local authorities [40 CFR 355.40].
The reportable quantity of vinylidene chloride is 100 pounds.
If an amount equal to or greater than this quantity is released
within a 24-hour period in a manner that will expose persons
outside the facility, employers are required to do the
following:
- Notify the National Response Center immediately at
(800) 424-8802 or at (202) 426-2675 in Washington, D.C. [40 CFR
302.6].
* 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 vinylidene chloride per calendar year or
otherwise use 10,000 pounds or more of vinylidene chloride 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 vinylidene chloride 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. Vinylidene chloride is listed as a hazardous
waste under RCRA and has been assigned EPA Hazardous Waste No.
U078. It is approved for land disposal after treatment and only
if the concentration of vinylidene chloride in the waste or
treatment residual does not exceed 33 mg/kg.
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
(703) 412-9810 (in the Washington, D.C. area) 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 vinylidene chloride 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 vinylidene chloride. 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 vinylidene chloride.
The resistance of various materials to permeation by vinylidene
chloride is shown below:
Material |
Breakthrough time (hr) |
responder |
>4(*) |
polyvinyl alcohol |
>4 |
teflon |
>4 |
butyl rubber |
<1(**) |
natural rubber |
<1(**) |
neoprene |
<1(**) |
nitrile rubber |
<1(**) |
polyvinyl chloride |
<1(**) |
viton |
<1(**) |
(*) Material has been estimated (but not tested) to provide
resistance to permeation for at least four hours.
(**) Not recommended, degradation may occur. |
To evaluate the use of these materials with vinylidene chloride,
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 vinylidene chloride.
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 other 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.
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