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 This information may be superseded by new developments in the field of industrial hygiene.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 FORMIC ACID
INTRODUCTION
This guideline summarizes pertinent information about formic acid for
workers and employers as well as for physicians, industrial hygienists, and
other occupational safety and health professionals who may need such
information to conduct effective occupational safety and health programs.
Recommendations may be superseded by new developments in these fields;
readers are therefore advised to regard these recommendations as general
guidelines and to determine whether new information is available.
SUBSTANCE IDENTIFICATION
* Formula
CH(2)O(2)
* Structure
(For Structure, see paper copy)
* Synonyms
Formic acid 85%, formic acid 90%, formic acid 95%, hydrogen
carboxylic acid, methanoic acid, aminic acid, formylic acid, Bilorin,
Collo-didax, Formira, Formisotin
* Identifiers
1. CAS No.: 64-18-6
2. RTECS No.: LQ4900000
3. DOT UN: 1779 60
4. DOT label: Corrosive
* Appearance and odor
Formic acid is a colorless, fuming liquid with a highly pungent,
penetrating odor. The usual commercial product is a solution of 90 percent
formic acid in water. The air odor threshold concentration for formic acid
is 49 parts per million (ppm) parts of air.
CHEMICAL AND PHYSICAL PROPERTIES
* Physical data
1. Molecular weight: 46.03
2. Boiling point (at 760 mm Hg): 101 degrees C (213.8 degrees F)
3. Specific gravity (water = 1): 1.22 at 20 degrees C (68 degrees F)
(glacial)
4. Vapor density: 1.6 (glacial)
5. Melting point: 8.4 degrees C (47.1 degrees F) (glacial)
6. Vapor pressure at 20 degrees C (68 degrees F): 35 mm Hg
7. Solubility: Miscible in water in all proportions; also miscible with
alcohol, ether, acetone, benzene, and glycerol.
8. Evaporation rate (butyl acetate = 1): 2.1
* Reactivity
1. Conditions contributing to instability: Heat or flame.
2. Incompatibilities: Contact between formic acid and strong oxidizers,
alkaline materials, or strong caustics should be avoided. Contact with
concentrated sulfuric acid causes formation of carbon monoxide. May explode
when in contact with hydrogen peroxide and with furfuryl alcohol.
3. Hazardous decomposition products: None reported.
4. Special precautions: Glacial formic acid will slowly decompose at room
temperatures resulting in increased pressure if containers are sealed or
unvented.
* Flammability
The National Fire Protection Association has assigned a flammability
rating of 2 (moderate fire hazard) to formic acid.
1. Flash point: 68.9 degrees C (156 degrees F) (open cup)
2. Autoignition temperature: 539 degrees C (1004 degrees F) (glacial)
3. Flammable limits in air (percent by volume): Lower, 18; upper, 57
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 formic acid.
Fires involving formic acid 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 formic acid 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. Firefighters should wear a full set of protective clothing and
self-contained breathing apparatus when fighting fires involving formic
acid.
EXPOSURE LIMITS
* OSHA PEL
The current Occupational Safety and Health Administration (OSHA)
permissible exposure limit (PEL) for formic acid is 5 ppm parts of air (9
milligrams 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 formic acid of 5 ppm
(9 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 formic acid a threshold limit value (TLV) of 5 ppm (9.4
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 10 ppm (19 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. 22].
* Rationale for Limits
The NIOSH limit is based on the risk of severe irritation of the
eyes, mucous membranes, upper respiratory tract, and skin [NIOSH
1992].
The ACGIH limits are based on the risk of irritation of the eyes,
skin, and respiratory tract [ACGIH 1991, p. 692].
HEALTH HAZARD INFORMATION
* Routes of Exposure
Exposure to formic acid can occur through inhalation, ingestion, and
eye or skin contact [Sittig 1991, p. 840].
* Summary of toxicology
1. Effects on Animals: Formic acid is severely irritating to the eyes,
skin, and mucous membranes. The oral LD(50) in rats is 1,100 mg/kg and 700
mg/kg in mice [NIOSH 1992]. A dose of 610 mg formic acid applied to a
rabbit's open skin produced mild irritation. A dose of 122 mg applied to the
eye of a rabbit caused severe irritation [Sax and Lewis 1989]. Instillation
of 10 percent formic acid solution in the eye of a rabbit caused an immediate
dense, white, local opacification of the cornea that cleared slightly after 5
days. Application of pure liquid formic acid, however, caused immediate,
local corneal opacification as well as opacification of the lens,
inflammation of the iris, and damage to the anterior chamber of the eye [NLM
1992]. Administration of formic acid in a monkey's eye produced the same
type of optic atrophy and blindness as that caused by exposure to methanol
[Grant 1986]. Intravenous doses of formic acid of 0.46 to 1.25 g/kg given to
rabbits caused central nervous system depression, vasoconstriction, and
diuresis. Intravenous doses of 4 mg/kg caused convulsions and death in
rabbits and methemoglobinuria in dogs [NLM 1992]. Studies of chronic
exposure to formic acid have shown that young rats given 0.5 or 1 percent
formic acid in their diets or drinking water for 6 weeks had reductions in
their rates of body weight gain and reduced organ size when compared with
controls [NLM 1992]. No histopathologic changes were noted in mice whose
ears had been painted with an 8-percent formic acid solution in water for up
to 50 days [Clayton and Clayton 1982]. Formic acid was not teratogenic after
injection of doses as great as 20 mg into fertilized chick eggs [Clayton and
Clayton 1982]. Formic acid is mutagenic in some, but not all, bacterial
species and in Drosophila germ cells [Clayton and Clayton 1982].
2. Effects on Humans: Formic acid is dangerously irritating to the skin,
eyes, and mucous membranes and may also be toxic to the kidneys. Workers
exposed to formic acid in a textile plant complained of nausea at an average
formic acid concentration of 15 ppm [NLM 1992]. Atmospheric concentrations as
low as 32 mg/l may be corrosive; however, a dilute solution of 10 percent
formic acid apparently is not corrosive [Clayton and Clayton 1982]. Acute,
overexposure to formic acid causes corrosion of the skin, eyes, and mucous
membrane of the mouth, throat, and esophagus and may be associated with
complications such as cardiovascular collapse and ischemic damage to the
heart, liver and kidneys, swelling of the airway, and respiratory distress.
Ingesting causes ulceration of the gastrointestinal tract, which results in
perforation and peritonitis and late scarring of structures of the
gastrointestinal tract which, in turn, produces obstructions that require
surgical repair [Gosselin 1984]. A worker splashed in the face with formic
acid developed respiratory distress and difficulty in swallowing, and died
within 6 hours [Hathaway et al. 1991]. Other reports indicate that splashes
of formic acid in the eye have caused permanent clouding of the cornea, with
loss of visual acuity. In one case, the injury required removal of the
affected eye [Grant 1986]. Chronic absorption of formic acid may cause
damage to the kidneys, which is indicated by albuminuria and hematuria [NLM
1992]. Chronic skin contact may cause sensitization dermatitis, particularly
in workers previously sensitized to formaldehyde [NLM 1992].
* Signs and symptoms of exposure
1. Acute exposure: Symptoms of acute exposure include redness, swelling,
and blistering of the skin and mucous membranes of the mouth and throat, eye
irritation, nausea, vomiting, diarrhea, difficulty in swallowing, difficulty
in breathing, headache, dizziness, blood in the urine, decreased or absence
of urine production, and unconsciousness. Signs of shock and impending
cardiovascular collapse including clammy skin, a weak and rapid pulse,
shallow respirations, and scanty or absent urine production.
2. Chronic exposure: Signs and symptoms of chronic exposure may include
kidney damage, dermatitis, and skin sensitization.
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 formic acid and lead to worker
exposures to this substance:
* The manufacture and transportation of formic acid * Use in natural
and synthetic textile and paper dyeing and finishing, as a dye-exhausting
agent, to impart finishes to cotton and wool, and as a shrink- and
wrinkle-proofing compound * Use as a chemical intermediate for formates,
oxalic acid, and performic acid; as a strong reducing agent for acids, salts,
dyes, fumigants, insecticides, refrigerants, and pharmaceuticals; and as a
solvent for perfumes and lacquers * Use in leather processing industry as
a deliming agent and neutralizer, and to tan, dehair, and plump hides *
Use in rubber industry as a coagulant for natural rubber latex and form
making, and as a preservative of latex * Use in electroplating industry to
control particle size and plating thickness, as a reducing agent in chrome
dyeing and in nickel plating baths, and in silvering glass * Use as an
antiseptic in wine and beer brewing, as a flavor adjunct in perfumes, and as
a preservative in animal feed additives and in cleaning solution compounds *
Use in miscellaneous operations as a wire stripping compound and to prepare
bare wires for soldering; as a laundry sour; as an oil well acidifying agent;
as an antiseptic in brewing; and in ore flotation
Methods that are effective in controlling worker exposures to formic acid,
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 formic acid 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
formic acid, 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 formic acid 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, and 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 formic acid exposure. The interviews, examinations,
and medical screening tests should focus on identifying the adverse effects
of formic acid on the eyes, skin, and 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 formic acid.
WORKPLACE MONITORING AND MEASUREMENT
Determination of a worker's exposure to airborne formic acid 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 48
liters is reached. The sample is then treated with 0.01N NaOH. Analysis is
conducted by ion chromatography. This method is partially validated and is
described in the OSHA Computerized Information System [OSHA 1994] and a
similar method is described in NIOSH Method No. 2011 [NIOSH 1994b].
PERSONAL HYGIENE PROCEDURES
If formic acid contacts the skin, workers should flush the affected areas
immediately with plenty of water, followed by washing with soap and water.
Clothing contaminated with formic acid 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 formic acid, particularly its potential for causing severe
irritation.
A worker who handles formic acid 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 formic acid or a solution containing formic
acid is handled, processed, or stored.
STORAGE
Formic acid 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 formic acid should
be protected from physical damage and ignition sources, and should be stored
separately from strong oxidizers, alkaline materials, strong caustics,
concentrated sulfuric acid, hydrogen peroxide, and furfuryl alcohol.
SPILLS AND LEAKS
In the event of a spill or leak involving formic acid, 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 the area of the spill or leak.
4. Do not touch the spilled material; stop the leak if it is possible to
do so without risk.
5. For small liquid spills, take up with vermiculite, dry sand, earth or
other noncombustible absorbent material and place into closed containers for
later 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
Formic acid 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 formic acid is 5,000 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 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
formic acid 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. formic acid is listed as a hazardous
waste under RCRA and has been assigned EPA Hazardous Waste No. U123. This
substance has been banned from land disposal until treated by fuel
substitution or incineration.
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 formic acid 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 formic acid. 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
formic acid. The resistance of various materials to permeation by formic
acid is shown below:
Material |
Breakthrough time (hr) |
|
Butyl Rubber |
>8 |
Saranex |
>8 |
Barricade |
>8 |
Chemrel |
>8 |
Responder |
>8 |
Neoprene |
>4 |
Polyvinyl Chloride |
>4 |
Natural Rubber |
Caution 1 to 4 |
Nitrile Rubber |
Caution 1 to 4 |
Viton |
Caution 1 to 4 |
4H (PE/EVAL) |
Caution 1 to 4 |
Polyethylene |
<1(*) |
Polyvinyl Alcohol |
<1(*) |
(*) Not recommended, degradation may occur
To evaluate the use of these PPE materials with formic acid, 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 formic acid.
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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