Disclaimer: These guidelines were developed under contract using generally accepted secondary sources. The protocol used by the contractor for surveying these data sources was developed by the National Institute for Occupational Safety and Health (NIOSH), the Occupational Safety and Health Administration (OSHA), and the Department of Energy (DOE). The information contained in these guidelines is intended for reference purposes only. None of the agencies have conducted a comprehensive check of the information and data contained in these sources. It provides a summary of information about chemicals that workers may be exposed to in their workplaces. The secondary sources used for supplements 111 and 1V were published before 1992 and 1993, respectively, and for the remainder of the guidelines the secondary sources used were published before September 1996. This information may be superseded by new developments in the field of industrial hygiene. Therefore readers are advised to determine whether new information is available.
OCCUPATIONAL SAFETY AND HEALTH GUIDELINE FOR CHLORODIPHENYL (54% CHLORINE)
INTRODUCTION
This guideline summarizes pertinent information about chlorodiphenyl (54%
chlorine) 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 Recommendations may be superseded by new developments in these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(12)H(5)Cl(5) (approximately)
* Structure
(For Structure, see paper copy)
* Synonyms
Polychlorinated biphenyl, PCB, chlorinated diphenyl, polychlorinated
polyphenyl, arochlor 1254, aroclor 1254, askarel
* Identifiers
1. CAS No.: 11097-69-1
2. RTECS No.: TQ1360000
3. DOT UN: 2315 31
4. DOT label: Class 9 (miscellaneous hazardous material)
* Appearance and odor
Chlorodiphenyl (54% chlorine) is a pale yellow, viscous liquid with
a mild hydrocarbon odor. Production and sale of chlorodiphenyls was halted
in 1977, but these substances are still found in transformers and
capacitors.
CHEMICAL AND PHYSICAL PROPERTIES
* Physical data
1. Molecular weight: 326 (approximately)
2. Boiling point (at 760 mm Hg): 365-390 degrees C (689-734 degrees F)
3. Specific gravity: Data not available.
4. Vapor density: Data not available.
5. Melting/Freezing point: Data not available.
6. Vapor pressure at 20 degrees C (68 degrees F): Data not available.
7. Solubility: Insoluble in water; soluble in most organic solvents.
8. Evaporation rate: Data not available.
* Reactivity
1. Conditions contributing to instability: Exposure to fire conditions
may cause the formation of a black soot containing polychlorinated
dibenzofurans and chlorinated benzo-p-dioxins.
2. Incompatibilities: Contact between chlorodiphenyl (54% chlorine) and
strong oxidizing agents may cause fires and explosions.
3. Hazardous decomposition products: Toxic gases and vapors such as
hydrogen chloride, chlorinated dibenzofurans, chlorinated phenols,
chlorinated naphthalenes, and carbon monoxide may be released in a fire
involving chlorodiphenyl (54% chlorine).
4. Special precautions: None reported.
* Flammability
The National Fire Protection Association has not assigned a
flammability rating to chlorodiphenyl (42% chlorine). Other sources list the
PCBs as combustible materials.
1. Flash point: Data not available.
2. Autoignition temperature: Data not available.
3. Flammable limits in air: Data not available.
4. Extinguishant: For small fires use dry chemical, carbon dioxide, water
spray, or regular foam. Use water spray, fog, or regular foam to fight large
fires involving chlorodiphenyl (54% chlorine).
Fires involving chlorodiphenyl (54% chlorine) should be fought
upwind from the maximum distance possible. Keep unnecessary people away;
isolate the hazard area and deny entry. Containers of chlorodiphenyl (54%
chlorine) should be moved from the fire area if it is possible to do so
safely. Do not scatter spilled materials with high-pressure water streams.
Dike fire control water for later disposal. Firefighters should wear a full
set of protective clothing and self-contained breathing apparatus when
fighting fires involving chlorodiphenyl (54% chlorine).
EXPOSURE LIMITS
* OSHA PEL
The current Occupational Safety and Health Administration (OSHA)
permissible exposure limit (PEL) for chlorodiphenyl (54% chlorine) is 0.5
milligram per cubic meter (mg/m(3)) of air as an 8-hour time-weighted average
(TWA) concentration. The OSHA PEL also bears a "Skin" notation, which
indicates that the cutaneous route of exposure (including mucous membranes
and eyes) contributes to overall exposure [29 CFR 1910.1000, Table
Z-].
* NIOSH REL
The National Institute for Occupational Safety and Health (NIOSH)
has established a recommended exposure limit (REL) for chlorodiphenyl (54%
chlorine) of 0.001 mg/m(3) as a TWA for up to a 10-hour workday and a 40-hour
workweek. NIOSH considers chlorodiphenyl (54% chlorine) a potential
occupational carcinogen [NIOSH 1992].
* ACGIH TLV
The American Conference of Governmental Industrial Hygienists
(ACGIH) has assigned chlorodiphenyl (54% chlorine) a threshold limit value
(TLV) of 0.5 mg/m(3) as a TWA for a normal 8-hour workday and a 40-hour
workweek. The ACGIH also assigns a "Skin" notation to chlorodiphenyl (54%
chlorine)] [ACGIH 1994, p. 16].
* Rationale for Limits
The NIOSH limit is based on the risk of skin, liver, and
reproductive effects, and on the potential for cancer; also on based on
tumors of the liver and pituitary gland and leukemias noted in animals [NIOSH
1992].
The ACGIH limit is based on the risk of systemic toxicity [ACGIH
1991, p. 286].
HEALTH HAZARD INFORMATION
* Routes of Exposure
Exposure to chlorodiphenyl (54% chlorine) can occur through
inhalation, ingestion, eye or skin contact, and absorption through the skin
[Sittig 1991].
* Summary of toxicology
1. Effects on Animals: Chlorodiphenyl (54% chlorine) is a carcinogen in
animals; it causes liver and bladder tumors. Chlorodiphenyl (54% chlorine)
is also a liver and reproductive toxin. Chlorodiphenyl is poorly metabolized
and tends to accumulate in lipid-rich tissues, such as brain tissue. The
more highly chlorinated PCBs, such as 54 percent chlorodiphenyl, have greater
carcinogenic potential than the less chlorinated chlorodiphenyls [Hathaway et
al. 1991]. This substance is toxic to the liver, causing fatty degeneration,
cell death, hypertrophy, and induction of microsomal enzymes [Hathaway et al.
1991]. The oral LD(50) in rats is 1010 mg/kg, and the intravenous LD(50) in
the same species is 358 mg/kg [NIOSH 1995]. The minimum lethal dermal dose
in rabbits is 1.5 g/kg [Hathaway et al. 1991]. Repeated dosing with
chlorodiphenyl (54% chlorine) caused bladder tumors in rats [Gosselin 1984].
Dietary administration of 54% chlorine chlorodiphenyl to mice and rats has
caused a significant excess of benign and malignant liver tumors in several
bioassays. Rats also developed interstitial metaplasia and a low,
statistically nonsignificant incidence of stomach adenocarcinomas [IARC
1987]. The International Agency for Research on Cancer has concluded that
there is sufficient evidence of the carcinogenic risk of chlorodiphenyl (54%
chlorine) in animals [IARC 1987]. Chlorodiphenyl (54% chlorine) is mutagenic
in mammalian test systems [NIOSH 1995].
2. Effects on Humans: Exposure to chlorodiphenyl (54% chlorine) causes
chloracne, eye and mucous membrane irritation, and liver damage. It may also
be a potential occupational carcinogen. Workers exposed to chlorodiphenyl
(54% chlorine) in electrical capacitor filling and sealing operations have
shown a slight increase in the incidence of cancer, particularly melanomas of
the skin; another study showed an excess number of deaths due to cancer of
the liver and biliary passages in chlorodiphenyl-exposed workers [IARC 1987].
A study of workers in Italy who had been exposed to a mixture of
chlorodiphenyl (54% and 42% chlorine) showed a significant increase in cancer
mortality; male workers had a significant excess of gastrointestinal tract
tumors (including a liver tumor) and female workers had a significant
increase in death from hematological tumors [IARC 1987]. The International
Agency for Research on Cancer (IARC) has concluded that the available studies
suggest an association between cancer and exposure to PCBs. IARC notes that
the increased risk from hepatobiliary cancer was consistent across different
studies [IARC 1987]. Workers exposed to concentrations below 1 mg/m(3) for
several months developed eczema, skin burning and systemic effects
[Parmeggiani 1983]. Studies of occupationally exposed persons have shown
evidence of liver injury when tested by serum enzyme studies or other liver
function tests; deaths due to toxic hepatitis have also been reported
[Gosselin 1984].
* Signs and symptoms of exposure
1. Acute exposure: Exposure to chlorodiphenyl (54% chlorine) cause
irritation and burning of the eyes and irritation of the nose, throat, and
skin. It may also cause headache, jaundice, vomiting, nausea, edema of the
facial skin, depression, dizziness, and abdominal pain.
2. Chronic exposure: Chronic exposure to chlorodiphenyl (54% chlorine)
causes chloracne, eczema, liver dysfunction, and peripheral neuropathies.
Exposure may also cause cancer (especially melanoma), gastrointestinal tract
tumors, and hematopoietic tumors.
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 chlorodiphenyl (54% chlorine) and lead
to worker exposures to this substance:
* Used in transformers * Used in heat transfer systems and hydraulic
systems * Used in and liberated during servicing of electromagnets,
switches, voltage regulators, capacitors, circuit breakers, reclosers, and
cable * Used on compressors and in the liquid of natural gas pipelines *
Used as a microscopic mounting medium, as an immersion oil in fluorescence
microscopy, and as an optical liquid * Used in research and development *
Used in carbonless copy paper
Methods that are effective in controlling worker exposures to chlorodiphenyl
(54% chlorine), 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 chlorodiphenyl (54% chlorine) 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
chlorodiphenyl (54% chlorine), 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 skin, blood, and liver.
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 chlorodiphenyl (54% chlorine) 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 skin, blood, or
liver.
* 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 chlorodiphenyl (54% chlorine) exposure. The
interviews, examinations, and medical screening tests should focus on
identifying the adverse effects of chlorodiphenyl (54% chlorine) on the skin,
blood, or liver. 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.
Chlorodiphenyl (54% chlorine) can be detected in the blood, plasma, or
adipose tissue of exposed individuals. There is apparently a close
correlation between the degree and duration of exposure and the blood
concentration of chlorodiphenyl in exposed workers. The upper limit of the
normal concentration of chlorodiphenyl in blood is 200 micrograms per liter
in occupationally exposed workers. Plasma concentrations also show good
correlation with occupational exposure; plasma concentration above 2 to 4
microgram per liter indicate significant exposure.
WORKPLACE MONITORING AND MEASUREMENT
Determination of a worker's exposure to airborne chlorodiphenyl (54%
chlorine) is made using an OSHA Versatile Sampler (OVS-2) 13 mm XAD-2 tube
(270/140 mg sections, 20/60 mesh) with a glass fiber filter enclosed. Samples
are collected at a maximum flow rate of 1.0 liter/minute until a maximum
collection volume of 60 liters is reached. Analysis is conducted by gas
chromatography using an electron capture detector (GC/ECD). This method is
described in the OSHA Computerized Information System [OSHA 1994] and is
partially validated. NIOSH has a similar method (Method No. 5503) for the
sampling and analysis of polychlorobiphenyls [NIOSH 1994b].
PERSONAL HYGIENE PROCEDURES
If chlorodiphenyl (54% chlorine) contacts the skin, workers should flush the
affected areas immediately with plenty of water, followed by washing with
soap and water.
Clothing contaminated with chlorodiphenyl (54% chlorine) 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 chlorodiphenyl (54% chlorine),
particularly its potential for causing systemic toxicity through dermal
absorption.
A worker who handles chlorodiphenyl (54% chlorine) 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 chlorodiphenyl (54% chlorine) or a solution
containing chlorodiphenyl (54% chlorine) is handled, processed, or stored.
STORAGE
Chlorodiphenyl (54% chlorine) 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
chlorodiphenyl (54% chlorine) should be protected from physical damage and
should be stored separately from strong oxidizing agents.
SPILLS AND LEAKS
In the event of a spill or leak involving chlorodiphenyl (54% chlorine),
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. Notify safety personnel.
2. Remove all sources of heat and ignition.
3. NUMBERED TEXT =Ventilate potentially explosive atmospheres.
4. Do not touch the spilled material; stop the leak if it is possible to
do so without risk.
5. Use non-sparking tools.
6. For small liquid 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 chlorodiphenyl (54% chlorine) 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
Chlorodiphenyl (54% chlorine) 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 chlorodiphenyl (54% chlorine) is 1 pound.
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 are not required by EPA in 40 CFR Part 372.30 to submit a
Toxic Chemical Release Inventory form (Form R) to EPA reporting the amount of
chlorodiphenyl (54% chlorine) 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 chlorodiphenyl (54% chlorine) 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 (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 chlorodiphenyl (54% chlorine) 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 chlorodiphenyl (54% chlorine). 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 chlorodiphenyl (54% chlorine). The resistance of various
materials to permeation by chlorodiphenyl (54% chlorine) is shown below:
Material |
Breakthrough time (hr) |
|
butyl rubber |
>8 |
neoprene |
>8 |
teflon |
>8 |
viton |
>8 |
saranex |
>8 |
barricade |
>8 |
chemrel |
>8 |
responder |
>8 |
4H (PE/EVAL) |
>4 |
nitrile rubber |
Caution 1 to 4 |
natural rubber |
<1(*) |
polyethylene |
<1(*) |
(*) Not recommended, degradation may occur
To evaluate the use of these PPE materials with chlorodiphenyl (54%
chlorine), 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 chlorodiphenyl (54% chlorine).
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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Baselt RC [1988]. Biological monitoring methods for industrial chemicals.
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