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 This information may be superseded by new developments in the field of industrial hygiene.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 ALPHA-CHLOROACETOPHENONE
INTRODUCTION
This guideline summarizes pertinent information about
alpha-chloroacetophenone 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 Recommendations may be superseded by new developments in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(8)H(7)ClO
* Structure
(For Structure, see paper copy)
* Synonyms
Phenacyl chloride, omega-chloroacetophenone, 2-chloroacetophenone,
chloromethyl phenyl ketone, phenyl chloromethyl ketone, tear gas, CN,
mace.
* Identifiers
1. CAS No.: 532-27-4
2. RTECS No.: AM6300000
3. DOT UN: 1697 55
4. DOT label: Poison * Appearance and odor
alpha-Chloroacetophenone is a colorless to gray solid with an
irritating floral odor. It has an air odor threshold of 0.035 part per
million (ppm) parts of air.
CHEMICAL AND PHYSICAL PROPERTIES
* Physical data
1. Molecular weight: 154.59
2. Boiling point (at 760 mm Hg): 247 degrees C (476.6 degrees F)
3. Specific gravity: 1.324 at 15 degrees C (59 degrees F) (solid)
4. Vapor density (air = 1): 5.32
5. Melting point: 58 to 59 degrees C (136.4 to 138.2 degrees F)
6. Vapor pressure at 20 degrees C (68 degrees F): 5.4 x 10(-3) mm Hg
7. Solubility: Practically insoluble in water; freely soluble in alcohol,
ether, and benzene.
8. Evaporation rate: Data not available.
* Reactivity
1. Conditions contributing to instability: Heat.
2. Incompatibilities: Contact between alpha-chloroacetophenone and water
or steam may cause generation of hydrogen chloride. alpha-Chloroacetophenone
is also incompatible with strong oxidizers and reacts slowly with metals,
causing mild corrosion.
3. Hazardous decomposition products: Toxic and corrosive gases and vapors
such as carbon monoxide and fumes of chlorine may be released when
alpha-chloroacetophenone undergoes thermal decomposition .
4. Special precautions: alpha-Chloroacetophenone will slowly corrode
metals.
* Flammability
The National Fire Protection Association has assigned a flammability
rating of 1 (slight fire hazard) to alpha-chloroacetophenone.
1. Flash point: 118 degrees C (244.4 degrees F) (closed cup)
2. Autoignition temperature: Data not available.
3. Flammable limits in air: Data not available.
4. Extinguishant: For small fires use dry chemical, water spray, or
regular foam. Use water spray, fog, or regular foam to fight large fires
involving alpha-chloroacetophenone .
Fires involving alpha-chloroacetophenone should be fought upwind
from the maximum distance possible. Keep unnecessary people away; isolate
the hazard area and deny entry. Emergency personnel should stay out of low
areas and ventilate closed spaces before entering. Containers of
alpha-chloroacetophenone 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. Dike fire
control water for later disposal; do not scatter this material. Firefighters
should wear a full set of protective clothing and self-contained breathing
apparatus when fighting fires involving alpha-chloroacetophenone.
EXPOSURE LIMITS
* OSHA PEL
The current Occupational Safety and Health Administration (OSHA)
permissible exposure limit (PEL) for alpha-chloroacetophenone is 0.05 ppm
(0.3 milligram per cubic meter (mg/m(3))) 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
alpha-chloroacetophenone of 0.05 ppm (0.3 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 alpha-chloroacetophenone a threshold limit value (TLV)
of 0.05 ppm (0.32 mg/m(3)) as a TWA for a normal 8-hour workday and a 40-hour
workweek [ACGIH 1994, p. 16].
* Rationale for Limits
The NIOSH limit is based on the risk of eye and upper respiratory
irritation, and possible conjunctivitis and corneal damage [NIOSH
1992].
The ACGIH limit is based on the risk of irritation, sensitization,
and possible systemic effects [ACGIH 1991, p. 266].
HEALTH HAZARD INFORMATION
* Routes of Exposure
Exposure to alpha-chloroacetophenone can occur through inhalation,
ingestion, and eye or skin contact [Sittig 1991].
* Summary of toxicology
1. Effects on Animals: alpha-Chloroacetophenone is a severe eye irritant
and lacrimator in experimental animals. The oral LD(50) values in rats,
rabbits, and guinea pigs are 50, 118, and 158 mg/kg, respectively [NLM 1995].
The short-term inhalation toxicity of alpha-chloroacetophenone is less
severe in mice than in rats, rabbits, or guinea pigs. Death occurred as a
result of asphyxia following lung damage resulting from pulmonary congestion,
hemorrhage and edema. Animals exposed to alpha-chloroacetophenone by
inhalation experienced lacrimation, salivation, lethargy, and labored
breathing [ACGIH 1991]. Instillation of 1 to 10 percent solution of
alpha-chloroacetophenone in polyethylene glycol into the eyes of rabbits
produced inflammation, corneal damage, keratitis, and increases in corneal
thickness and intraocular tension [NLM 1995]. Topical or intradermal
administration of alpha-chloroacetophenone in guinea pigs caused erythema,
edema, induration, necrosis and eschar formation [ACGIH 1991]. Laboratory
animals exposed to high concentrations (not further specified) developed
systemic effects including agitation, miosis, coma, areflexia, and fatty
infiltration of the liver [Gosselin 1984].
2. Effects on Humans: alpha-Chloroacetophenone is a potent lacrimating
agent and an eye and respiratory tract irritant in humans [Hathaway et al.
1991]. Burning and irritation of the skin can occur especially if the skin
is moist. Contact sensitization has been reported [Hathaway et al. 1991].
The use of alpha-chloroacetophenone as a riot-control agent has caused
several deaths; the estimated lethal concentration in humans is 8,500
mg-min/m(3) for 10 minutes [ACGIH 1991]. Although the corneal haziness,
pain, and severe irritation associated with most exposures are reversible,
overexposure can cause permanent partial opacity [ACGIH 1991]. Severe
inhalation exposure causes pulmonary edema, which may have delayed onset
[ACGIH 1991].
* Signs and symptoms of exposure
1. Acute exposure: Acute exposure to alpha-chloroacetophenone results in
tearing, burning of the eyes, blurred vision, irritation of the nose, runny
nose, and burning of the throat. Skin contact may result in redness,
irritation and dermatitis. Pulmonary congestion and edema may result and
death from acute exposure has occurred [ACGIH 1991; Sittig 1991; Gosselin
1984; Hathaway et al. 1991].
2. Chronic exposure: Chronic exposure to alpha-chloroacetophenone can
result in allergic sensitization and contact dermatitis [Hathaway et al.
1991].
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 alpha-chloroacetophenone and lead to
worker exposures to this substance:
* The manufacture and transportation of alpha-chloroacetophenone *
Liberated during loading of solutions for aerosols for law enforcement and
civilian protective devices; use as a riot-control agent (Mace); use in
chemical warfare * Use as a pharmaceutical intermediate
Methods that are effective in controlling worker exposures to
alpha-chloroacetophenone, 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 alpha-chloroacetophenone 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
alpha-chloroacetophenone, 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 eyes,
skin, and respiratory system. 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 alpha-chloroacetophenone 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 eyes, skin, or respiratory
system.
* 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 alpha-chloroacetophenone exposure. The interviews,
examinations, and medical screening tests should focus on identifying the
adverse effects of alpha-chloroacetophenone on the eyes, skin, or respiratory
system. 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 alpha-chloroacetophenone.
WORKPLACE MONITORING AND MEASUREMENT
Determination of a worker's exposure to airborne alpha-chloroacetophenone is
made using a two Tenax-GC tubes in series (first tube 35 mg section, second
tube 17 mg section). Samples are collected at a maximum flow rate of 0.2
liter/minute until a maximum collection volume of 12 liters is reached. The
sample is then treated with methanol. Analysis is conducted by high
performance liquid chromatography using an ultraviolet detector (HPLC/UV).
This method (OSHA modified NIOSH method # 291) is described in the OSHA
Computerized Information System [OSHA 1994] and is partially validated.
PERSONAL HYGIENE PROCEDURES
If alpha-chloroacetophenone contacts the skin, workers should flush the
affected areas immediately with plenty of water for at least 15 minutes,
followed by washing with soap and water.
Clothing contaminated with alpha-chloroacetophenone 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 alpha-chloroacetophenone,
particularly its potential for severe irritation.
A worker who handles alpha-chloroacetophenone 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 alpha-chloroacetophenone or a solution
containing alpha-chloroacetophenone is handled, processed, or stored.
STORAGE
alpha-Chloroacetophenone 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
alpha-chloroacetophenone should be protected from physical damage and
moisture, and should be stored separately from strong oxidizers. Conveying
equipment and storage containers should be electrically grounded during
transfer to prevent the possibility of a dust explosion. All electrical
service should be non-sparking and have an explosion-proof design. Any bulk
storage system should have an explosion-relief design. Empty containers
contain residues of alpha-chloroacetophenone and should be handled
accordingly.
SPILLS AND LEAKS
In the event of a spill or leak involving alpha-chloroacetophenone, persons
not wearing protective equipment and fully-encapsulating, vapor-protective
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. Absorb small quantities of alpha-chloroacetophenone with sand or other
noncombustible absorbent material and place in containers for later disposal.
5. For small dry spills, use a clean shovel and place the material into a
clean, dry container; cover and remove the container from the spill area.
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 alpha-chloroacetophenone 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
alpha-Chloroacetophenone 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 alpha-chloroacetophenone 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 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
alpha-chloroacetophenone per calendar year or otherwise use 10,000 pounds or
more of alpha-chloroacetophenone 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 alpha-chloroacetophenone 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 alpha-chloroacetophenone 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 alpha-chloroacetophenone 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 alpha-chloroacetophenone. 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 alpha-chloroacetophenone. The resistance of one PPE material to
permeation by alpha-chloroacetophenone is shown below:
Material |
Breakthrough time (hr) |
|
responder |
>8 |
To evaluate the use of this or other PPE materials with alpha-
chloroacetophenone, 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 alpha-chloroacetophenone.
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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