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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 This information may be superseded by new developments in the field of industrial hygiene.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 COBALT METAL, DUST, AND FUME
(As Co)
INTRODUCTION
This guideline summarizes pertinent information about cobalt metal, dust,
and fume 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 Recommendations may be superseded by new developments in these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.
APPLICABILITY
The general guidelines contained in this document apply to the metal,
cobalt, and the dust and fumes of several cobalt compounds, such as cobaltous
oxide, cobaltic oxide, and cobaltic-cobaltous oxide. When specific data are
available, this guideline identifies the form of cobalt (metal, dust, or
fume) or the compound to which the information applies.
SUBSTANCE IDENTIFICATION
* Formula
Co; CoO; Co(2)O(2); CO(2)O(4)
* Structure
Structures vary depending on specific compound.
* Synonyms
Synonyms vary depending on specific compound.
* Identifiers
1. CAS No.: 7440-48-4 (metal)
2. RTECS No.: GF8750000 (metal)
3. Specific DOT UN: None.
4. Specific DOT label: None.
* Appearance and odor
Cobalt is a silvery, bluish-white, odorless, and magnetic metal.
The fume and dust of cobalt metal is odorless and black. The appearance and
odor of cobalt compounds and their dusts and fumes vary with the
compound.
CHEMICAL AND PHYSICAL PROPERTIES
* Physical data
1. Atomic weight: 58.9 (metal)
2. Boiling point (at 760 mm Hg): 3100 to 3200 degrees C (5612 to 5792
degrees F) (metal)
3. Specific gravity (water = 1): 8.92 (metal) at 20 degrees C (68 degrees
F)
4. Vapor density: Not applicable.
5. Melting point: 1493 degrees C (2719.4 degrees F) (metal)
6. Vapor pressure at 20 degrees C (68 degrees F): Data not available.
7. Solubility: Insoluble in water; soluble in nitric acid and other acids.
8. Evaporation rate (butyl acetate = 1): Not applicable.
* Reactivity
1. Conditions contributing to instability: None reported.
2. Incompatibilities: Contact between cobalt metal in powdered form and
fused ammonium nitrate, hydrozinium nitrate, or strong oxidizing agents
should be avoided. Ignites on contact with bromide pentafluoride. Powdered
cobalt ignites spontaneously in air.
3. Hazardous decomposition products: None reported.
4. Special precautions: None reported.
* Flammability
The National Fire Protection Association has not assigned a
flammability rating to cobalt metal, dust, and fume; however, powdered cobalt
(pyrophoric cobalt) is combustible and burns brilliantly in air at room
temperature. Dusts of cobalt metal or cobalt compounds may form explosive
mixtures in air.
1. Flash point: Data not available.
2. Autoignition temperature: Data not available.
3. Flammable limits in air: Data not available.
4. Extinguishant: Do not use water; dry sand, dry dolomite, dry graphite
powder, or sodium chloride have been recommended for fighting fires involving
cobalt.
Fires involving cobalt metal, dust, and fume should be fought upwind
from the maximum distance possible. Isolate the hazard area and deny access
to unnecessary personnel. Firefighters should wear a full set of protective
clothing and self-contained breathing apparatus when fighting fires involving
cobalt metal, dust, and fume.
EXPOSURE LIMITS
* OSHA PEL
The current Occupational Safety and Health Administration (OSHA)
permissible exposure limit (PEL) for cobalt metal, dust, and fume (as Co) is
0.1 milligram per cubic meter (mg/m(3)) of air as an 8-hour time-weighted
average (TWA) concentration [29 CFR 1910.1000, Table Z-1].
* NIOSH REL
The National Institute for Occupational Safety and Health (NIOSH)
has established a recommended exposure limit (REL) for cobalt metal, dust,
and fume of 0.05 mg/m(3) as a TWA for up to a 10-hour workday and a 40-hour
workweek [NIOSH 1992].
* ACGIH TLV
The American Conference of Governmental Industrial Hygienists
(ACGIH) has assigned cobalt, elemental, and inorganic compounds (as Co) a
threshold limit value (TLV) of 0.02 mg/m(3) as a TWA for a normal 8-hour
workday and a 40-hour workweek. The ACGIH also lists these substances as
animal carcinogens (A3 substances) [ACGIH 1994, p. 17].
* Rationale for Limits
The NIOSH limit is based on the risk of dermatitis, and the
potential for pulmonary fibrosis [NIOSH 1992].
The ACGIH limit is based on the risk of pulmonary effects.
HEALTH HAZARD INFORMATION
* Routes of Exposure
Exposure to cobalt metal fume and dust can occur through inhalation,
ingestion, and eye or skin contact [Sittig 1991].
* Summary of toxicology
1. Effects on Animals: Cobalt metal, dust, and fume are pulmonary toxins
and respiratory and skin sensitizers. The oral LD(50) in rats is 6,171
mg/kg. Rats injected intramuscularly with the powder of cobalt metal or
cobalt oxide developed malignancies of the skeletal muscle [Hathaway et al.
1991]. Oral exposure of rats to 1,500 mg cobalt metal was lethal to all
animals. All rats fed 30 mg cobalt metal per day for 1 month also died
[Clayton and Clayton 1982]. Guinea pigs developed obstructive inflammation
of the lung, pneumonitis, pleural effusions, and inflammation of the
pericardial sac following intratracheal injection of cobalt metal or a
mixture of 25 percent cobalt metal and 75 percent tungsten carbide. These
pathological changes were often rapidly fatal [Clayton and Clayton 1982].
Miniature swine exposed daily by inhalation to 0.1 mg/m(3) of a cobalt metal
dust developed pulmonary disease within three months [ACGIH 1991]. Chronic
exposures to 20 mg/m(3) of a cobalt metal blend produced focal fibrosis and
granulomas of the lungs and hyperplastic changes in the mucosa lining the
smaller airways [Clayton and Clayton 1982]. High doses of cobalt also caused
foci of cell death and diffuse degenerative changes in heart muscle
[Parmeggiani 1983]. Cobalt metal introduced into the eyes of rabbits resulted
in irritation and the development of abscesses that involved intraocular
structures [Grant 1986].
2. Effects on Humans: Inhalation of cobalt metal fume and dust may cause
interstitial fibrosis, interstitial pneumonitis, myocardial and thyroid
disorders, and sensitization of the respiratory tract and skin [Hathaway et
al. 1991; Parmeggiani 1983]. Chronic cobalt poisoning may also produce
polycythemia and hyperplasia of the bone marrow [NLM 1995]. Among the 12
workers engaged in the manufacture or grinding of tungsten carbide tools
(cobalt is used as a binder for tungsten carbide crystals), who developed
interstitial lung disease, there were eight fatalities [Hathaway et al.
1991]. A 16.6 percent incidence of skin sensitivity to cobalt was found in
patch testing of cement workers in Finland. A review of 14 other reports on
European cement workers showed a 25 percent average incidence of
sensitization [Clayton and Clayton 1982]. Acute forms of cardiomyopathy,
hypothyroidism, and thyroid hyperplasia were seen in Canada after cobalt was
added to beer to stabilize the foam. Myocardial disorders have also been
observed in cobalt production workers [NLM 1995].
* Signs and symptoms of exposure
1. Acute exposure: Acute exposure to cobalt metal, dust, and fume is
characterized by irritation of the eyes and, to a lesser extent, irritation
of the skin [Sittig 1991]. In sensitized individuals, exposure causes an
asthma-like attack, with wheezing, bronchospasm, and dyspnea [Hathaway et al.
1991]. Ingestion of cobalt may cause nausea, vomiting, diarrhea, and a
sensation of hotness [Sittig 1991; Sax and Lewis 1989].
2. Chronic exposure: Chronic exposure to cobalt metal, dust, or fume may
cause respiratory or dermatologic signs and symptoms. Following skin
sensitization, contact with cobalt causes eruptions of dermatitis in creases
and on frictional surfaces of the arms, legs, and neck [Genium 1988].
Following sensitization of the respiratory system, cobalt exposure causes an
obstructive lung disease with wheezing, cough, and shortness of breath
[Parmeggiani 1983; NJDH 1985]. Chronic respiratory exposure results in
reduced lung function, increased fibrotic changes on chest X-ray, production
of scanty mucoid sputum, and shortness of breath. Chronic cobalt poisoning
may cause polycythemia, hyperplasia of the bone marrow and thyroid gland,
pericardial effusion, and damage to the alpha cells of the pancreas [NLM
1995].
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 cobalt metal, dust, and fume and lead
to worker exposures to this substance:
* The manufacture and transportation of cobalt metal, dust, and fume *
Liberated during use as a binder in manufacture of cemented carbide items,
during the grinding of cemented carbide and steel tools, and during the
preparation of alloys and cobalt salts * Liberated during synthesis of
cobalt compounds for use in the electroplating, ceramics, glass, photography,
enamels, and pigment industries; used as driers and catalysts * Liberated
during manufacture of metal items from cutting tool and tool steels, from
hardfacing alloys, from magnetic alloys, and from super- and high-temperature
alloys; during manufacture of items containing low-expansion alloys and
constant-modulus alloys; during manufacture of metal-to-glass seals in
electric lamps, vacuum tubes, and X-ray tubes * Liberated during
manufacture of permanent and soft magnets, and dental prosthetic and
osteosynthetic items; during asbestos fiber processing * Used in jet
engines, cobalt and hydrogen bombs, nuclear technology, experimental
medicine, cancer research, and cancer treatment * Used as trace element in
fertilizers, as an additive in cattle feed, and in the manufacture of lamp
filaments
Methods that are effective in controlling worker exposures to cobalt metal,
dust, and fume, 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 cobalt metal, dust, and fume 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
cobalt metal, dust, and fume, 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 respiratory system and skin. Medical surveillance for respiratory
disease should be conducted using the principles and methods recommended by
the American Thoracic Society.
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 cobalt metal, dust, and fume 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 respiratory system or
skin.
* 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 cobalt metal, dust, and fume exposure. The
interviews, examinations, and medical screening tests should focus on
identifying the adverse effects of cobalt metal, dust, and fume on the
respiratory system or skin. 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 cobalt metal, dust, and fume 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.
Cobalt can be detected in the urine of exposed workers using atomic
absorption spectroscopy. End-of-shift urine cobalt concentrations were found
to correlate well with worker's exposure in a hard metal manufacturing plant.
Urinary cobalt concentrations ranged from 1 to 35 microgram per liter of
urine for airborne cobalt levels of 2.5 to 105 micrograms per cubic
meter.
WORKPLACE MONITORING AND MEASUREMENT
Determination of a worker's exposure to airborne cobalt metal, dust, or fume
(as Co) is made using a mixed cellulose ester filter (MCEF), 0.8 microns.
Samples are collected at a maximum flow rate of 2.0 liters/minute until a
minimum collection volume of 480 liters or a maximum collection volume of 960
liters is reached. Analysis is conducted by atomic absorption spectroscopy
(AAS). This method (OSHA ID-121) is fully validated and is described in the
OSHA Computerized Information System [OSHA 1994]. NIOSH has also published a
similar method (Method No. 7027) that can be used to determine a worker's
exposure to cobalt metal, dust, or fume [NIOSH 1994b].
PERSONAL HYGIENE PROCEDURES
If cobalt metal or dust contacts the skin, workers should immediately wash
the affected areas with soap and water.
Clothing contaminated with cobalt metal or dust 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 cobalt metal, dust, and fume,
particularly its potential for causing eye and skin irritation.
A worker who handles cobalt metal or dust 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 cobalt metal, dust, or fume or a solution
containing cobalt metal or dust is handled, processed, or stored.
STORAGE
Cobalt metal dust (powdered metal) 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 cobalt metal dust should be protected from physical damage and
ignition sources, and should be stored separately from strong oxidizers.
SPILLS AND LEAKS
In the event of a spill or leak involving cobalt metal or dust, 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. Ventilate potentially explosive atmospheres.
4. Do not touch the spilled material.
5. For small dry spills, use a vacuum or a wet mop to clean up spill. If
these are not available, use a clean shovel and place the material into a
clean, dry container; cover and remove the container from the spill area.
6. For large spills, wet down with water and build dikes far ahead of the
spill to contain the cobalt metal or dust 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
Cobalt metal, dust, and fume 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].
Employers are not required by the emergency release notification
provisions in 40 CFR Part 355.40 to notify the National Response Center of an
accidental release of cobalt metal, dust, and fume; 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
cobalt metal, dust, and fume per calendar year or otherwise use 10,000 pounds
or more of cobalt metal, dust, and fume 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 cobalt metal, dust, and fume 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 cobalt metal, dust, and fume 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 cobalt metal, dust, and fume 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 cobalt metal, dust, and fume. 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 cobalt metal, dust, and fume. There are no published reports on
the resistance of various materials to permeation by cobalt metal, dust, and
fume.
To evaluate the use of PPE materials with cobalt metal, dust, and fume,
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 cobalt metal, dust, and fume.
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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