California Code of Regulations › Title 8 - Industrial Relations › Division 1 - Department of Industrial Relations › Chapter 4 - Division of Industrial Safety › Subchapter 7 - General Industry Safety Orders › Group 16 - Control of Hazardous Substances › Article 110 - Regulated Carcinogens › Appendix A to Section 5217 - Substance Technical Guidelines for Formalin

Current through Register 2024 Notice Reg. No. 28, July 12, 2024
The following Substance Technical Guideline for
						  Formalin provides information on uninhibited formalin solution
						  (37%formaldehyde, no methanol stabilizer). It is designed to inform employees
						  at the production level of their rights and duties under the formaldehyde
						  standard whether their job title defines them as workers or supervisors. Much
						  of the information provided is general; however, some information is specific
						  for formalin. When employee exposure to formaldehyde is from resins capable of
						  releasing formaldehyde, the resin itself and other impurities or decomposition
						  products may also be toxic, and employers should include this information as
						  well when informing employees of the hazards associated with the materials they
						  handle. The precise hazards associated with exposure to formaldehyde depend
						  both on the form (solid, liquid, or gas) of the material and the concentration
						  of formaldehyde present. For example, 37-50 percent solutions of formaldehyde
						  present a much greater hazard to the skin and eyes from spills or splashes than
						  solutions containing less than 1 percent formaldehyde. Individual Substance
						  Technical Guidelines used by the employer for training employees should be
						  modified to properly give information on the material actually being
						  used.
Substance Identification
Chemical Name: Formaldehyde
Chemical Family: Aldehyde
Chemical Formula: HCHO Molecular Weight: 30.03
Chemical Abstracts Service Number
(CAS Number): 50-00-0
Synonyms: Formalin; Formic
Aldehyde; Paraform; Formol; Formalin
(Methanol-free); Fyde; Formalith;
Methanal; Methyl Aldehyde; Methylene
Glycol; Methylene Oxide;
Tetraoxymethalene; Oxomethane;
Oxymethylene
Components and Contaminants
Percent: 37.0 Formaldehyde
Percent: 63.0 Water
(NOTE: Inhibited solutions contain methanol.)
Other Contaminants: Formic Acid (alcohol free)
Exposure Limits: OSHA TWA-0.75 ppm
OSHA STEL-2 ppm
Physical Data
Description: Colorless liquid, pungent odor
Boiling Point: 214° F (101°C)
Specific Gravity: 1.08 (H2O =
						  1@20° C)
pH: 2.8-4.0
Solubility in Water: Miscible
Solvent Solubility: Soluble in alcohol and
						  acetone
Vapor Density: 1.04 (Air = 1@20° C)
Odor Threshold: 0.8-1 ppm
Fire and Explosion Hazard
Moderate fire and explosion hazard when exposed to heat
						  or flame.
The flash point of 37% formaldehyde solutions is above
						  normal room temperature, but the explosion range is very wide, from 7 to 73% by
						  volume in air.
Reaction of formaldehyde with nitrogen dioxide,
						  nitromethane, perchloric acid and aniline, or peroxyformic acid yields
						  explosive compounds.
Flash Point: 1855F (85°C) closed cup
Lower Explosion Limit: 7%
Upper Explosion Limit: 73%
Autoignition Temperature: 806°F (430°C)
Flammability Class (OSHA): Category 4 flammable
						  liquid
Extinguishing Media: Use dry chemical, "alcohol foam,"
						  carbon dioxide, or water in flooding amounts as fog. Solid streams may not be
						  effective. Cool fire-exposed containers with water from side until well after
						  fire is out.
Use of water spray to flush spills can also dilute the
						  spill to produce nonflammable mixtures. Water runoff, however, should be
						  contained for treatment. National Fire Protection Association section
						  325 M Designation:
Health: 2--Materials hazardous to health, but areas may
						  be entered with full-faced mask self-contained breathing apparatus which
						  provides eye protection.
Flammability: 2--Materials which must be moderately
						  heated before ignition will occur. Water spray may be used to extinguish the
						  fire because the material can be cooled below its flash point.
Reactivity: D--Materials which (in themselves) are
						  normally stable even under fire exposure conditions which are not reactive with
						  water. Normal fire fighting procedures may be used. Reactivity
Stability: Formaldehyde solutions may self-polymerize
						  to form paraformaldehyde which precipitates.
Incompatibility (Materials to Avoid): Strong oxidizing
						  agents, caustics, strong alkalies, isocyanates, anhydrides, oxides, and
						  inorganic acids. Formaldehyde reacts with hydrochloric acid to form the potent
						  carcinogen, bischloromethyl ether. Formaldehyde reacts with nitrogen dioxide,
						  nitromethane, perchloric acid and aniline, or peroxyformic acid to yield
						  explosive compounds. A violent reaction occurs when formaldehyde is mixed with
						  strong oxidizers.
Hazardous Combustion or Decomposition Products: Oxygen
						  from the air can oxidize formaldehyde to formic acid, especially when heated.
						  Formic acid is corrosive.
Health Hazard Data
Acute Effects of Exposure
Ingestion (Swallowing): Liquids containing 10 to 40%
						  formaldehyde cause severe irritation and inflammation of the mouth, throat, and
						  stomach. Severe stomach pains will follow ingestion with possible loss of
						  consciousness and death. Ingestion of dilute formaldehyde solutions
						  (0.03-0.04%) may cause discomfort in the stomach and pharynx.
Inhalation (Breathing): Formaldehyde is highly
						  irritating to the upper respiratory tract and eyes. Concentrations of 0.5 to
						  2.0 ppm may irritate the eyes, nose, and throat of some individuals.
						  Concentrations of 3 to 5 ppm also cause tearing of the eyes and are intolerable
						  to some persons. Concentrations of 10 to 20 ppm cause difficulty in breathing,
						  burning of the nose and throat, cough, and heavy tearing of the eyes, and 25 to
						  30 ppm causes severe respiratory tract injury leading to pulmonary edema and
						  pneumonitis. A concentration of 100 ppm is immediately dangerous to life and
						  health. Deaths from accidental exposure to high concentrations of formaldehyde
						  have been reported.
Skin (Dermal): Formalin is a severe skin irritant and a
						  sensitizer. Contact with formalin causes white discoloration, smarting, drying,
						  cracking, and scaling. Prolonged and repeated contact can cause numbness and a
						  hardening or tanning of the skin. Previously exposed persons may react to
						  future exposure with an allergic eczematous dermatitis or hives.
Eye Contact: Formaldehyde solutions splashed in the eye
						  can cause injuries ranging from transient discomfort to severe, permanent
						  corneal clouding and loss of vision. The severity of the effect depends on the
						  concentration of formaldehyde in the solution and whether or not the eyes are
						  flushed with water immediately after the accident.
NOTE: The perception of formaldehyde by odor and eye
						  irritation becomes less sensitive with time as one adapts to formaldehyde. This
						  can lead to overexposure if a worker is relying on formaldehyde's warning
						  properties to alert him or her to the potential for exposure.
Acute Animal Toxicity:
Oral, rats: LD50 = 800 mg/kg
Oral, mouse: LD50 = 42 mg/kg
Inhalation, rats: LCLo = 250 mg/kg
Inhalation, mouse: LCLo = 900 mg/kg
Inhalation, rats: LC50 = 590 mg/kg
Chronic Effects of Exposure
Carcinogenicity: Formaldehyde has the potential to
						  cause cancer in humans. Repeated and prolonged exposure increases the risk.
						  Various animal experiments have conclusively shown formaldehyde to be a
						  carcinogen in rats. In humans, formaldehyde exposure has been associated with
						  cancers of the lung, nasopharynx and oropharynx, and nasal passages.
Mutagenicity: Formaldehyde is genotoxic in several in
						  vitro test systems showing properties of both an initiator and a
						  promoter.
Toxicity: Prolonged or repeated exposure to
						  formaldehyde may result in respiratory impairment. Rats exposed to formaldehyde
						  at 2 ppm developed benign nasal tumors and changes of the cell structure in the
						  nose as well as inflamed mucous membranes of the nose. Structural changes in
						  the epithelial cells in the human nose have also been observed. Some persons
						  have developed asthma or bronchitis following exposure to formaldehyde, most
						  often as the result of an accidental spill involving a single exposure to a
						  high concentration of formaldehyde.
Emergency and First Aid Procedures
Ingestion (Swallowing): If the victim is conscious,
						  dilute, inactivate, or absorb the ingested formaldehyde by giving milk,
						  activated charcoal, or water. Any organic material will inactivate
						  formaldehyde. Keep affected person warm and at rest. Get medical attention
						  immediately. If vomiting occurs, keep head lower than hips.
Inhalation (Breathing): Remove the victim from the
						  exposure area to fresh air immediately. Where the formaldehyde concentration
						  may be very high, each rescuer must put on a self-contained breathing apparatus
						  before attempting to remove the victim, and medical personnel should be
						  informed of the formaldehyde exposure immediately. If breathing has stopped,
						  give artificial respiration. Keep the affected person warm and at rest.
						  Qualified first-aid or medical personnel should administer oxygen, if
						  available, and maintain the patient's airway and blood pressure until the
						  victim can be transported to a medical facility. If exposure results in a
						  highly irritated upper respiratory tract and coughing continues for more than
						  10 minutes, the worker should be hospitalized for observation and
						  treatment.
Skin Contact. Remove contaminated clothing (including
						  shoes) immediately. Wash the affected area of your body with soap or mild
						  detergent and large amounts of water until no evidence of the chemical remains
						  (at least 10 to 20 minutes). If there are chemical burns, get first aid to
						  cover the area with sterile, dry dressing, and bandages. Get medical attention
						  if you experience appreciable eye or respiratory irritation.
Eye Contact: Wash the eyes immediately with large
						  amounts of water occasionally lifting lower and upper lids, until no evidence
						  of chemical remains (at least 15 to 20 minutes). In case of burns, apply
						  sterile bandages loosely without medication. Get medical attention immediately.
						  If you have experienced appreciable eye irritation from a splash or excessive
						  exposure, you should be referred promptly to an ophthalmologist for
						  evaluation.
Emergency Procedures
Emergencies: If you work to an area where a large
						  amount of formaldehyde could be released in an accident or from equipment
						  failure, your employer must develop procedures to be followed in event of an
						  emergency. You should be trained in your specific duties in the event of an
						  emergency, and it is important that you clearly understand these duties.
						  Emergency equipment must be accessible and you should be trained to use any
						  equipment that you might need. Formaldehyde contaminated equipment must be
						  cleaned before reuse.
If a spill of appreciable quantity occurs, leave the
						  area quickly unless you have specific emergency duties. Do not touch spilled
						  material. Designated persons may stop the leak and shut off ignition sources if
						  these procedures can be done without risk. Designated persons should isolate
						  the hazard area and deny entry except for necessary people protected by
						  suitable protective clothing and respirators adequate for the exposure. Use
						  water spray to reduce vapors. Do not smoke, and prohibit all flames or flares
						  in the hazard area.
Special Firefighting Procedures: Learn procedures and
						  responsibilities in the event of a fire in your workplace. Become familiar with
						  the appropriate equipment and supplies and their location. In firefighting,
						  withdraw immediately in case of rising sound from venting safety device or any
						  discoloration of storage tank due to fire.
Spill, Leak, and Disposal Procedures
Occupational Spill: For small containers, place the
						  leaking container in a well ventilated area. Take up small spills with
						  absorbent material and place the waste into properly labeled containers for
						  later disposal. For larger spills, dike the spill to minimize contamination and
						  facilitate salvage or disposal. You may be able to neutralize the spill with
						  sodium hydroxide or sodium sulfite. Your employer must comply with EPA rules
						  regarding the clean-up of toxic waste and notify state and local authorities,
						  if required. If the spill is greater than 1,000 lb/day, it is reportable under
						  EPA's Superfund legislation.
Waste Disposal: Your employer must dispose of waste
						  containing formaldehyde in accordance with applicable local, state, and Federal
						  law and in a manner that minimizes exposure of employees at the site and of the
						  clean-up crew.
Monitoring and Measurement Procedures
Monitoring Requirements: If your exposure to
						  formaldehyde exceeds the 0.5 ppm action level or the 2 ppm STEL, your employer
						  must monitor your exposure. Your employer need not measure every exposure if a
						  "high exposure" employee can be identified. This person usually spends the
						  greatest amount of time nearest the process equipment. If you are a
						  "representative employee," you will be asked to wear a sampling device to
						  collect formaldehyde. This device may be a passive badge, adsorbent tube
						  attached to a pump, or an impinger containing liquid. You should perform your
						  work as usual, but inform the person who is conducting the monitoring of any
						  difficulties you are having wearing the device.
Evaluation of 8-hour Exposure: Measurements taken for
						  the purpose of determining time-weighted average (TWA) exposures are best taken
						  with samples covering the full shift. Samples collected must be taken from the
						  employee's breathing zone air.
Short-term Exposure Evaluation: If there are tasks that
						  involve brief but intense exposure to formaldehyde, employee exposure must be
						  measured to assure compliance with the STEL. Sample collections are for brief
						  periods, only 15 minutes, but several samples may be needed to identify the
						  peak exposure.
Monitoring Techniques: OSHA's only requirement for
						  selecting a method for sampling and analysis is that the methods used
						  accurately evaluate the concentration of formaldehyde in employees' breathing
						  zones. Sampling and analysis may be performed by collection of formaldehyde on
						  liquid or solid sorbents with subsequent chemical analysis. Sampling and
						  analysis may also be performed by passive diffusion monitors and short-term
						  exposure may be measured by instruments such as real-time continuous monitoring
						  systems and portable direct reading instruments.
Notification of Results: Your employer must inform you
						  of the results of exposure monitoring representative of your job. You may be
						  informed in writing, but posting the results where you have ready access to
						  them constitutes compliance with the standard.
Protective Equipment and Clothing
(Material impervious to formaldehyde is needed if the
						  employee handles formaldehyde solutions of 1% or more. Other employees may also
						  require protective clothing or equipment to prevent dermatitis.)
Respiratory Protection: Use NIOSH approved full
						  facepiece negative pressure respirators equipped with approved cartridges or
						  canisters within the use limitations of these devices. (Present restrictions on
						  cartridges and canisters do not permit them to be used for a full workshift.)
						  In all other situations, use positive pressure respirators such as the positive
						  pressure air purifying respirator or the self-contained breathing apparatus
						  (SCBA). If you use a negative pressure respirator, your employer must provide
						  you with fit testing of the respirator at least once a year in accordance with
						  the procedures outlined in Appendix E.
Protective Gloves: Wear protective (impervious) gloves
						  provided by your employer, at no cost, to prevent contact with formalin. Your
						  employer should select these gloves based on the results of permeation testing
						  and in accordance with the ACGIH Guidelines for Selection of Chemical
						  Protective Clothing.
Eye Protection: If you might be splashed in the eyes
						  with formalin, it is essential that you wear goggles or some other type of
						  complete protection for the eye. You may also need a face shield if your face
						  is likely to be splashed with formalin, but you must not substitute face
						  shields for eye protection. (This section pertains to formaldehyde solutions of
						  1% or more.)
Other Protective Equipment: You must wear protective
						  (impervious) clothing and equipment provided by your employer at no cost to
						  prevent repeated or prolonged contact with formaldehyde liquids. If you are
						  required to change into whole-body chemical protective clothing, your employer
						  must provide a change room for your privacy and for storage of your normal
						  clothing.
If you are splashed with formaldehyde, use the
						  emergency showers and eyewash fountains provided by your employer immediately
						  to prevent serious injury. Report the incident to your supervisor and obtain
						  necessary medical support.
Entry Into an IDLH Atmosphere
Enter areas where the formaldehyde concentration might
						  be 100 ppm or more only with complete body protection including a
						  self-contained breathing apparatus with a full facepiece operated in a positive
						  pressure mode or a supplied air respirator with full facepiece and operated in
						  a positive pressure mode. This equipment is essential to protect your life and
						  health under such extreme conditions.
Engineering Controls
Ventilation is the most widely applied engineering
						  control method for reducing the concentration of airborne substances in the
						  breathing zones of workers. There are two distinct types of ventilation.
Local Exhaust: Local exhaust ventilation is designed to
						  capture airborne contaminants as near to the point of generation as possible.
						  To protect you, the direction of contaminant flow must always be toward the
						  local exhaust system inlet and away from you.
General (Mechanical): General dilution ventilation
						  involves continuous introduction of fresh air into the workroom to mix with the
						  contaminated air and lower your breathing zone concentration of formaldehyde.
						  Effectiveness depends on the number of air changes per hour. Where devices
						  emitting formaldehyde are spread out over a large area, general dilution
						  ventilation may be the only practical method of control.
Work Practices: Work practices and administrative
						  procedures are an important part of a control system. If you are asked to
						  perform a task in a certain manner to limit your exposure to formaldehyde, it
						  is extremely important that you follow these procedures.
Medical Surveillance
Medical surveillance helps to protect employees'
						  health. You are encouraged strongly to participate in the medical surveillance
						  program.
Your employer must make a medical surveillance program
						  available at no expense to you and at a reasonable time and place if you are
						  exposed to formaldehyde at concentrations above 0.5 ppm as an 8-hour average or
						  2 ppm over any 15-minute period. You will be offered medical surveillance at
						  the time of your initial assignment and once a year afterward as long as your
						  exposure is at least 0.5 ppm (TWA) or 2 ppm (STEL). Even if your exposure is
						  below these levels, you should inform your employer if you have signs and
						  symptoms that you suspect, through your training, are related to your
						  formaldehyde exposure because you may need medical surveillance to determine if
						  your health is being impaired by your exposure.
The surveillance plan includes:
(a) A medical disease questionnaire.
(b) A physical examination if the physician determines
						  this is necessary.
If you are required to wear a respirator, your employer
						  must offer you a physical examination and a pulmonary function test every
						  year.
The physician must collect all information needed to
						  determine if you are at increased risk from your exposure to formaldehyde. At
						  the physician's discretion, the medical examination may include other tests,
						  such as a chest X-ray, to make this determination.
After a medical examination, the physician will provide
						  your employer with a written opinion which includes any special protective
						  measures recommended and any restrictions on your exposure. The physician must
						  inform you of any medical conditions you have which would be aggravated by
						  exposure to formaldehyde.
All records from your medical examinations, including
						  disease surveys, must be retained at your employer's expense.
Emergencies
If you are exposed to formaldehyde in an emergency and
						  develop signs or symptoms associated with acute toxicity from formaldehyde
						  exposure, your employer must provide you with a medical examination as soon as
						  possible. This medical examination will include all steps necessary to
						  stabilize your health. You may be kept in the hospital for observation if your
						  symptoms are severe to ensure that any delayed effects are recognized and
						  treated.