| SECTION 1. CHEMICAL IDENTIFICATION
|CHEMINFO Record Number:
|CCOHS Chemical Name:
Formaldehyde (non-specific name)
|Chemical Name French:
|Chemical Name Spanish:
- Trade Name(s):
|CAS Registry Number:
|EU EINECS/ELINCS Number:
||Aliphatic aldehyde / saturated aliphatic aldehyde / saturated aliphatic monoaldehyde / alkanal / methanal
- Appearance and Odour:
- Colourless, sometimes milky, solution with a pungent odour.(45,87)
- Odour Threshold:
- The odour threshold varies between individuals and a wide range of values has been reported. Odour recognition has been reported to occur in the range of 0.027-1.9 ppm.(12)
- Warning Properties:
- POOR - odour may not be detected at the TLV.
- Formaldehyde is normally produced and sold as water solutions with concentrations ranging from 25-56 wt% formaldehyde gas.(1) The predominant grade sold is 37% by weight, known as formalin. Methanol is generally added as a stabilizer to prevent polymerization of the formaldehyde. Formaldehyde solutions are sold as low methanol (uninhibited) and high methanol (inhibited) grades. Depending on the grade, formaldehyde solutions may contain 0.5-15% methanol.(1) Other stabilizers used include other alcohols (e.g. ethanol, propanol or butanol), guanamines (e.g. isophthalobisguanamine), alkalenebis(melamines), melamine, hydroxypropylmethylcellulose, methyl- and ethylcelluloses or poly(vinyl alcohol)s at concentrations ranging from 10-1000 ppm.(1,7)
Formaldehyde is also available in solid form as the cyclic trimer, trioxane, and its polymer, paraformaldehyde.(7)
This CHEMINFO profile reviews the hazards and control measures for formaldehyde solutions. For information on formaldehyde gas, consult the CHEMINFO review of formaldehyde gas.
The presence of stabilizers in formaldehyde solutions can influence the overall hazards of the product. Consult the manufacturer/supplier Material Safety Data Sheet (MSDS) for additional information on ingredients. For information on the hazards and control measures for methanol, consult the CHEMINFO review of methanol.
- Uses and Occurrences:
- The largest use of formaldehyde is in the manufacture of urea-formaldehyde, phenolic, melamine and polyacetal resins. It is also used as a chemical intermediate for the manufacture of 1,4-butanediol, polyols (e.g. pentaerythritol and trimethylolpropane), hexamethylenetetramine, methylene diisocyanate (MDI), chelating agents (e.g. ethylenediaminetetracetic acid (EDTA) and nitrilotriacetic acid (NTA)), paraformaldehyde and methylene dianiline.
It is also used as a building block for products used to manufacture textile finishing agents; fire-retardant fabrics; crop protection agents; dyes; surface-active agents; processing aids; tanning agents; dispersion and plastics precursors; extraction agents; animal feeds; slow-release fertilizers; perfumes; vitamins; flavourings; and drugs. It is used in agriculture for seed treatment, soil disinfection, and as an insecticide and fumigant; as a reagent in analysis; to water- and grease-proof concrete and plaster; as a hydrogen sulfide scavenger; and biocide in oil production and in the rubber industry for latex; in the metal industry as a corrosion inhibitor, in mirror finishing and electroplating; as a preservative in consumer products (e.g. foods, cosmetics, household cleaning agents), as well as grains, seed dressings, wood, hides and skins; in room fumigants; in embalming fluids; in histopathology to preserve tissue specimens; as a bacteriostatic agent in some foods (e.g. cheese); in the photographic industry as a film hardener; for the electrodisposition of printed circuits; in paper treatment; as a starch modifier; and in the sugar industry to prevent bacterial growth during syrup recovery.(1,7,43,44,87)
Industrial release of formaldehyde gas can occur at any stage during the production, use, storage, transport or disposal of products containing formaldehyde.(45) For more information on the release of formaldehyde gas to indoor and outdoor environments from both natural and man-made processes, consult the CHEMINFO review of formaldehyde gas.
| SECTION 3. HAZARDS IDENTIFICATION
- EMERGENCY OVERVIEW:
- Colourless, sometimes milky, solution with a pungent odour. COMBUSTIBLE LIQUID AND GAS. Formaldehyde gas released from the solutions can form explosive mixtures with air at, or above 50-85 deg C depending on the amount of formaldehyde in the solution and the other components the formaldehyde solution. During a fire, flammable hydrogen gas and irritating and/or toxic gases may be generated. VERY TOXIC. May be fatal if inhaled, absorbed through the skin or swallowed. Gas is severely irritating to the eyes and upper respiratory tract. May damage the lining of the nasal cavity and the upper respiratory tract. Causes lung injury-effects may be delayed. CORROSIVE to the eyes and skin. Can cause permanent eye injury and severe burns. SKIN SENSITIZER. May cause severe allergic skin reaction. CANCER HAZARD - can cause cancer. POSSIBLE MUTAGEN - May cause genetic damage, based on animal information.
NOTE: Formaldehyde solutions contain other hazardous ingredients, e.g. methanol.
Effects of Short-Term (Acute) Exposure
- Formaldehyde solutions can release formaldehyde gas, which is extremely irritating and very toxic if inhaled, posing a very serious inhalation hazard. The amount of gas released depends on the concentration of formaldehyde and other ingredients present in the formulation.
The odour of formaldehyde gas can be recognized at concentrations as low as 0.03-1.9 ppm. It causes mild to moderate irritation of the nose and throat at 0.3-3 ppm.(3,43,59) Up to 20% of the population are more responsive and may react acutely to formaldehyde at very low concentrations (0.25 ppm).(4) Exposure to 10 ppm causes severe irritation of the upper respiratory tract, with a burning sensation of the nose and throat.(5) Other effects include coughing, choking and vomiting. Exposure to 50 ppm or higher may lead to inflammation of the lung (pneumonitis) or to a potentially fatal accumulation of fluid in the lungs (pulmonary edema).(60,61) Symptoms of pulmonary edema (chest pain and shortness of breath) can be delayed for up to 24 or 48 hours after exposure.
In a study of funeral home employees, exposure to 0.25-1.77 ppm formaldehyde produced nose irritation, sneezing, coughing, and headaches in an unspecified number of embalmers.(62) Thirty-three volunteers exposed to 0, 0.25, 0.5, 1 or 2 ppm formaldehyde (generated from heating paraformaldehyde) for 90 minutes experienced irritation of the nose and throat at all concentrations, with severity increasing with concentration.(63) In a study of 23 students exposed to 0.02 to 2.7 ppm (cited as 0.02 to 3.3 mg/m3) and phenol from cadavers, most experienced nose and throat irritation, headache, dizziness, and cough. Of 12 who had post-exposure testing, one showed a significant decrease in pulmonary function. The effects were attributed to the formaldehyde exposure.(64)
No case reports of death from inhalation exposure to formaldehyde were located, but deaths have been observed in animal studies following exposure to concentrations that would produce intolerable irritation.
- Skin Contact:
- Formaldehyde solutions are considered corrosive to the skin. However, they have only caused mild to moderate skin irritation in animal studies. There is little human information on the irritancy of formaldehyde solutions, although their potential for irritation is widely accepted.(19,41,44) Formaldehyde solutions form corrosive formic acid upon standing. Corrosive materials can cause severe burns, blistering and permanent scarring of the skin. Any skin contact may also involve inhalation exposure.
Skin contact with formaldehyde solutions can cause an allergic skin reaction in some people. Refer to skin sensitization under "Effects of long-term (chronic) exposure" for more information.
Formaldehyde solutions may be toxic if absorbed through the skin, based on an unconfirmed animal toxicity value.
- Eye Contact:
- Formaldehyde solutions are corrosive to the eye. Corrosive materials can cause severe eye damage with permanently altered vision or blindness. There are several case reports of eye injury occurring when formaldehyde solutions were accidentally splashed into the eyes. Characteristically, formaldehyde eye injuries are immediately painful but can leave the eye looking normal for at least an hour or two after exposure. Over the course of the next 12 hours, very severe eye damage becomes apparent.(20, unconfirmed)
Formaldehyde gas is also irritating to the eyes. The threshold for mild eye irritation may be as low as 0.01 ppm. Although, continued exposure may result in some acclimatization.(5) Twelve volunteers exposed for 5 minutes to formaldehyde (composition not specified), mixed with other non-irritating pollutants, could detect and react to 0.01 ppm, with 0.2 ppm causing light to medium eye irritation, and 0.6 ppm causing medium to severe irritation.(65) Exposure to 1 ppm formaldehyde gas (generated by heating paraformaldehyde) for 6 minutes caused slight to moderate eye irritation in 27 volunteers.(66) Thirty-three volunteers exposed to 0, 0.25, 0.5, 1 or 2 ppm formaldehyde gas (generated from heating paraformaldehyde) for 90 minutes experienced irritation of the eyes at all concentrations, with severity increasing with concentration.(63)
- Formaldehyde solutions are toxic if ingested, based on animal and human information. Ingestion of formalin (37-50% water solutions of formaldehyde; 0-15% methanol) in accidental, suicidal or homicidal cases, has caused corrosive burning of the mouth, throat and digestive tract with vomiting of tissue and blood.(5,67) Ingested formaldehyde is rapidly converted to formic acid, which can cause metabolic acidosis, and damage to the liver and kidneys leading to jaundice and swelling of body tissues. In severe cases, there may be convulsions, central nervous system depression and death.(67) The fatal dose for formaldehyde in humans is estimated to be about 60-90 mL of formalin (317-475 mg/kg of formaldehyde assuming a 37% solution of formalin and a 70 kg person).(68) The presence of methanol may contribute to the overall toxicity of ingested formalin. Ingestion is not a typical route of occupational exposure.
Effects of Long-Term (Chronic) Exposure
- Only very limited information is available on the potential effects from long-term occupational exposure to formaldehyde. Mixed exposures and/or low numbers of workers studied limit most of the available studies.
Occupational exposure studies indicate that formaldehyde exposure causes temporary reversible decreases in lung function but no long-term effects. There is sufficient evidence that formaldehyde causes nasopharyngeal cancer in humans. There is limited evidence for cancer of the nasal cavity and paranasal sinuses and strong but not sufficient evidence for leukemia (see "CARCINOGENICITY" below for more information). Formaldehyde is not a respiratory sensitizer, but can bring on the symptoms of asthma in susceptible individuals, probably due to irritation of the airways. Human and animal studies demonstrate that formaldehyde solutions cause skin sensitization.
Nervous system effects have been reported in studies of histology or anatomy technicians exposed to formaldehyde. However, firm conclusions cannot be drawn from these studies because of limitations such as concurrent exposures to other chemicals.
- Nervous System:
- Firm conclusions cannot be drawn about the potential nervous system effects of formaldehyde. Neurological impairment was reported in two studies of workers (usually histology and anatomy technicians) exposed to formaldehyde. In all cases, there was concurrent exposure to other solvents including phenol, xylene, chloroform and ethanol. A third study did not show any significant neurological effects in a large group of histology and anatomy technicians.
In a study of 305 female histology technicians, there was a significant correlation between self-reported hours of formaldehyde exposure and decreased performance in 6/10 neurobehavioural tests. The age range was 23-78 years (mean age 40), with average employment of 17 years. Specific exposure information was not available, but sampling conducted in 10 laboratories showed current concentrations of formaldehyde ranging from 0.2-1.9 ppm in tissue-dissecting areas, with a peak of 5 ppm in samples taken 14 inches from exposed formalin-fixed tissues. There were concurrent exposures to other chemicals including xylene, toluene and chloroform.(69) In a follow-up to this study, 318 histology technicians who were exposed to formaldehyde and to combinations of other solvents including xylene, ethanol and chloroform were evaluated for neurobehavioural effects over a 4-year period. No significant changes were noted.(70)
In a limited study, 3 anatomy technicians exposed to estimated concentrations of 0.1-5.8 ppm formaldehyde for 16-30 years, and 1 manufacturing worker exposed to unspecified concentrations of formaldehyde for 14 years were studied. In all cases, there was concurrent exposure to other chemicals. Two workers reported short-term, high-level formaldehyde exposure. Extensive neurobehavioural impairment was observed in all 4 workers and 2 had seizures, effects that were still present 4-7 years after exposure.(71) This study is limited by the very small number of workers evaluated and the concurrent exposure to other chemicals.
- Lungs/Respiratory System:
- Occupational exposure studies indicate that formaldehyde exposure causes temporary, reversible decreases in lung function, but no long-term effects. Formaldehyde is considered a probable respiratory carcinogen (see Carcinogenicity below).
Several studies have evaluated lung function in formaldehyde-exposed particle-board and plywood workers, workers using acid-hardening paints, embalmers, urea-formaldehyde resin producers, medical students and anatomy and histology workers. Exposures to formaldehyde ranged from less than 0.02 ppm to greater than 5 ppm and there were often concurrent exposures to other substances. In most of the studies, exposure caused temporary reversible decreases in lung function, but no long-term effects.(19)
In a study of 109 workers exposed to time-weighted-average concentrations of 0.17-2.93 ppm (average 0.69 ppm) formaldehyde for up to 20 years, there were no significant differences in lung function measured at the beginning of the shift compared to 254 controls. These measurements were thought to reflect the lack of any chronic effects from long-term formaldehyde exposure.(72)
In a study of 47 carpentry workers exposed to 0.04-1.62 ppm (average 0.42 ppm) for an average of 5.9 years, there was no significant difference in lung function measured Monday morning before work compared to 20 controls.(73)
- Respiratory Sensitization:
- There is very little convincing evidence that formaldehyde can induce asthma, given the small number of reported cases in relation to the large number of workers potentially exposed to formaldehyde. Only a very few of the reported cases have proven positive in well-conducted bronchial challenge tests. There is generally little correspondence between the presence of formaldehyde-specific antibodies and the occurrence of asthmatic symptoms in exposed people. However, the evidence indicates that formaldehyde can bring on the symptoms of asthma in susceptible individuals, probably through irritation of the airways.(74)
- Long-term exposure to formaldehyde solutions is expected to cause dry, red, irritated skin (dermatitis).
- Skin Sensitization:
- Formaldehyde solutions cause occupational skin sensitization. Once a person is sensitized, contact with even a small amount of a formaldehyde solution can cause outbreaks of dermatitis with symptoms such as redness, rash, itching and swelling. This reaction can spread from the hands or arms to the face and body.
Many cases of allergic contact dermatitis have been associated with exposure to formaldehyde solutions. Occupational examples include nurses, funeral embalmers and newsprint handlers.(59,75) In over 4700 consecutive patients patch tested with an extended standard series of up to 34 chemicals, formaldehyde was the ninth most common cause of allergic reactions, with positive reactions in 3% of the patients.(76) It is estimated that 3-6% of the population responds positively to 2% formaldehyde.(59) Studies in guinea pigs and mice also prove that formaldehyde solutions cause skin sensitization.
- Formaldehyde is carcinogenic to humans. The International Agency for Research on Cancer has concluded there is sufficient evidence that formaldehyde causes nasopharyngeal cancer in humans. There is limited evidence for cancer of the nasal cavity and paranasal sinuses and "strong but not sufficient evidence" for leukemia.(17) There are many human population studies on the increase of respiratory cancers in people occupationally exposed to formaldehyde. These studies have been extensively reviewed elsewhere and are not reviewed here.(3,4,5,19,43,44,45)
Excess numbers of nasopharyngeal cancers were associated with occupational exposure to formaldehyde in 2/6 cohort studies, 3/4 case-control studies, and in meta-analyses. In addition, 2/6 case-control studies indicated a positive association between occupational exposure to formaldehyde and cancer of the nasal cavities and paranasal sinuses, while 3 were negative and 1 was weakly positive. Cohort studies of embalmers and other professionals who use formaldehyde showed some excess risk for brain cancer. However, this risk did not increase with exposure. There was no increase in risk found for other types of cancer.(14,19) Some large scale, well-conducted studies have found an association between formaldehyde exposure and leukemia, while others have not.(100)
In a recent meta-analysis of the incidence of pancreatic cancer in 14 epidemiology studies, a small but consistent increase was found in studies of embalmers, anatomists and pathologists, but not in industrial workers, who had higher average and peak exposures. The increased incidence may be due to better diagnosis in the first group or to exposures to chemicals other than formaldehyde.(78)
- The International Agency for Research on Cancer (IARC) has concluded that this chemical is carcinogenic to humans (Group 1).
- The American Conference of Governmental Industrial Hygienists (ACGIH) has designated this chemical as a suspected human carcinogen (A2).
- The US National Toxicology Program (NTP) has listed this chemical as reasonably anticipated to be a human carcinogen.
- (formaldehyde gas)
- This chemical is regulated by the US Occupational Safety and Health Administration (OSHA) as a carcinogen.
- Teratogenicity and Embryotoxicity:
- The available human and animal evidence does not suggest that formaldehyde is a developmental toxin.
There are several human population studies of adverse pregnancy outcomes in women occupationally exposed to formaldehyde. Studies that found significantly higher rates of miscarriages in women occupationally exposed to formaldehyde are all limited by self-reporting of exposures and by the low number of women studied. The larger studies and those that determined formaldehyde exposure by evaluation of work task, have not shown an increased risk of miscarriage. No significant association between formaldehyde exposure and low birth weights (less than 2500 g) was found in 3 human population studies.(47)
There are many animal studies that have examined the potential developmental toxicity of formaldehyde. Many of these studies have limitations such as low animal numbers, lack of detailed information on methods, and lack of information on maternal toxicity. Well-conducted animal studies do not show developmental effects in the absence of maternal toxicity.
- Reproductive Toxicity:
- There is insufficient evidence to determine if formaldehyde causes reproductive toxicity.
In a retrospective study of women wood workers, 288 were not exposed to formaldehyde and 235 were subdivided into 119 low, 77 medium and 39 high formaldehyde exposure. Assignment to an exposure category was based on self-reporting verified with measured concentrations from own or a comparable workplace. In the high exposure group, formaldehyde exposure was associated with a longer time to pregnancy and an increased risk for endometriosis.(79) However, firm conclusions cannot be drawn from this study due to limitations such as self-reporting bias, the relatively small number of women studied and concurrent exposures to other potentially harmful chemicals.
In a study, which is not available in English, menstrual irregularities and higher infertility were reported in female workers exposed to formaldehyde, based on self-reporting and examinations.(5,47-unconfirmed) This study is limited by poorly reported methods, self-reporting biases, no accounting for confounding factors and no definition of infertility.
In a Finnish study of the effects of the father's occupation on the rate of miscarriage, formaldehyde exposure was not associated with an increase in miscarriages.(80)
Despite limitations, the few animal studies available do not suggest that formaldehyde exposure will affect fertility.
- Formaldehyde is considered mutagenic, based on positive results (e.g. chromosomal aberrations in lung cells) observed in studies with live animals. In occupational exposure studies, which are limited by such problems as low numbers of workers studied and mixed exposures, both positive and negative results (micronuclei, sister chromatid exchanges (SCEs), chromosome aberrations in lymphocytes or cheek and nose cells) and a negative result (abnormal sperm) were obtained.(19,44,46,81) However, positive results (SCEs in lymphocytes, DNA-protein crosslinks in lymphocytes) were obtained in 2 reasonably well-conducted studies.(81,82)
SCE rates in lymphocytes were studied in 142 hospital workers, 90 of who were exposed to formaldehyde (average exposure period 15.4 years) and 52 who were not exposed. Adjustments were made for age, sex, smoking habits, education years and origin. The average number of SCEs per chromosome and the average proportion of cells with a high number of SCEs (more than 8) were both significantly higher in exposed than in non-exposed workers. These 2 variables were also higher in workers with more than 15 years exposure in comparison to those with less than 15 years (significance not reported).(81) In a study of 186 hospital workers exposed to formaldehyde for an average of 16 years and 213 unexposed workers, there was a significantly increase in DNA-protein crosslinks in the lymphocytes of the exposed group. Adjustment was made for age, gender, smoking, education level and origin.(82)
- Toxicologically Synergistic Materials:
- Several animal studies have exposed animals to formaldehyde in combination with other carcinogens. In some of these studies, formaldehyde enhanced the effect of other carcinogens, causing more tumours or faster tumour growth.(19) Animal studies also suggest that formaldehyde may facilitate respiratory sensitization to other allergens.
- Potential for Accumulation:
- Formaldehyde does not accumulate. It is a normal intermediate metabolite and is found in all cells. It is very reactive and readily bonds to proteins and nucleic acids. It has a half-life in the blood of about 90 seconds and is rapidly metabolized to formic acid (which is excreted in the urine), converted to carbon dioxide (which is exhaled), or used to synthesize proteins and nucleic acids.(44,47,67)
- Health Comments:
- Formalin is 37-50% formaldehyde gas dissolved in water, often with 0.5-15% methanol added as a stabilizer. Therefore, possible methanol toxicity should be considered with exposures to Formalin. Consult the CHEMINFO review of methanol for additional information.
| SECTION 4. FIRST AID MEASURES
- This chemical is very toxic. Take proper precautions to ensure your own safety before attempting rescue (e.g. wear appropriate protective equipment, use the buddy system). Remove source of contamination or move victim to fresh air. If breathing is difficult, trained personnel should administer emergency oxygen. DO NOT allow victim to move about unnecessarily. Symptoms of pulmonary edema can be delayed up to 48 hours after exposure. Quickly transport victim to an emergency care facility.
- Skin Contact:
- Avoid direct contact. Wear chemical protective clothing, if necessary. As quickly as possible, remove contaminated clothing, shoes and leather goods (e.g. watchbands, belts). Immediately flush with lukewarm, gently flowing water for at least 30 minutes. DO NOT INTERRUPT FLUSHING. If necessary, and it can be done safely, continue flushing during transport to emergency care facility. Quickly transport victim to an emergency care facility.
Double bag, seal, label and leave contaminated clothing, shoes and leather goods at the scene for safe disposal.
- Eye Contact:
- Avoid direct contact. Wear chemical protective gloves, if necessary. Immediately flush the contaminated eye(s) with lukewarm, gently flowing water for at least 30 minutes, while holding the eyelid(s) open. If a contact lens is present, DO NOT delay irrigation or attempt to remove the lens. Neutral saline solution may be used as soon as it is available. DO NOT INTERRUPT FLUSHING. If necessary, continue flushing during transport to emergency care facility. Take care not to rinse contaminated water into the unaffected eye or onto the face. Quickly transport victim to an emergency care facility.
- NEVER give anything by mouth if victim is rapidly losing consciousness, is unconscious or convulsing. Have victim rinse mouth thoroughly with water. DO NOT INDUCE VOMITING. If vomiting occurs naturally, have victim rinse mouth with water again. Quickly transport victim to an emergency care facility.
- First Aid Comments:
- Provide general supportive measures (comfort, warmth, rest).
Consult a doctor and/or the nearest Poison Control Centre for all exposures.
Some first aid procedures recommended above require advanced first aid training. Protocols for undertaking advanced procedures must be developed in consultation with a doctor and routinely reviewed.
All first aid procedures should be periodically reviewed by a doctor familiar with the material and its conditions of use in the workplace.
- Note to Physicians:
- Formalin is 37-50% formaldehyde gas dissolved in water, often with 0.5-15% methanol added as a stabilizer. Therefore, possible methanol toxicity should be considered with exposures to Formalin. Consult the CHEMINFO review of methanol for additional information.
Other types of formaldehyde solutions may also contain other hazardous ingredients. Consult the Material Safety Data Sheet (MSDS) for complete ingredient information.
| SECTION 5. FIRE FIGHTING MEASURES
- Flash Point:
- 50 deg C (122 deg F) (closed cup) (37% formaldehyde, 15% methanol); 85 deg C (185 deg F) (closed cup) (37% formaldehyde, methanol free) (16)
- Lower Flammable (Explosive) Limit (LFL/LEL):
- 7% (gas) (16)
- Upper Flammable (Explosive) Limit (UFL/UEL):
- 73% (gas) (16)
- Autoignition (Ignition) Temperature:
- 430 deg C (806 deg F) (gas) (7,16)
- Sensitivity to Mechanical Impact:
- Not sensitive. Commercial solutions are stable.
- Sensitivity to Static Charge:
- Formaldehyde solutions will not accumulate static charge, since they have high dielectric constants. At room temperature, vapours released from formaldehyde/methanol mixtures may be ignited by a static discharge of sufficient energy. Vapour from formaldehyde solutions that are methanol free, will not be ignited by a static discharge at room temperature, since the flash point is high.
- Electrical Conductivity:
- Not available
- Minimum Ignition Energy:
- Not available
- Combustion and Thermal Decomposition Products:
- Carbon monoxide, carbon dioxide, hydrogen, formic acid, methanol and other toxic, irritating and flammable chemicals may be formed in a fire. Formaldehyde decomposes into methanol and carbon monoxide at temperatures above 150 deg C.(7,44) Above 350 deg C, it tends to decompose into carbon monoxide and hydrogen.(1,7)
- Fire Hazard Summary:
- COMBUSTIBLE LIQUID. Formaldehyde gas released from solutions can form explosive mixtures with air at, or above 50-85 deg C. During a fire, flammable hydrogen gas and irritating and/or toxic gases may be generated. Heat from a fire can cause a rapid build-up of pressure inside containers, which may cause explosive rupture and a sudden release of large amounts of flammable and very toxic gases.
NOTE: The fire properties of formaldehyde solutions depend on the concentration of formaldehyde and other ingredients present in the formulation (e.g. methanol or other alcohols). Consult the Material Safety Data Sheet (MSDS) for additional information.
- Extinguishing Media:
- Carbon dioxide, dry chemical powder, appropriate foam, water spray or fog. Special "alcohol resistant fire-fighting foams" are recommended for use with any polar liquid that is completely water soluble like formaldehyde solutions.(16) Fire fighting foam manufacturers should be consulted for recommendations regarding types of foams and application rates.
- Fire Fighting Instructions:
- Use extreme caution. Evacuate all personnel from the fire area. Decomposition may occur under fire conditions and may rupture containers releasing very toxic and flammable gases. Fight fire from a protected location or maximum possible distance. Approach fire from upwind to avoid extremely hazardous gas and decomposition products. Wear full protective suit if exposure is possible. See advice in Protection of Firefighters.
In the heat of a fire, formaldehyde gas may be produced when formaldehyde solutions are heated. If the gas is ignited, use fire-fighting procedures suitable for fighting formaldehyde gas fires. If the flow of gas from the solution cannot be stopped and there is no risk to the surrounding areas, allow the fire to continue burning while protecting exposed materials with water spray, to prevent ignition of other combustible materials. Gas clouds may be controlled by water spray or fog. The resulting water solutions of formaldehyde may be flammable and very toxic. Dike fire control water for appropriate disposal. See the CHEMINFO review on formaldehyde gas for additional information.
Closed containers may rupture violently when exposed to the heat of fire and suddenly release large amounts of products. Always stay away from ends of tanks, but be aware that flying material (shrapnel) from ruptured tanks may travel in any direction.
If possible, isolate materials not yet involved in the fire and move containers from fire area if this can be done without risk. Protect personnel. Otherwise, cool fire-exposed containers, tanks or equipment by applying hose streams. Cooling should begin as soon as possible (within several minutes) and should concentrate on any unwanted portions of the container. No part of a container should be subjected to a temperature higher than 50 deg C (approximately 122 deg F). Apply water from the side and a safe distance.
Cooling should continue until well after the fire is out. If this is not possible, use unmanned monitor nozzles and immediately evacuate the area.
If a leak or spill has not ignited, use water spray to flush spills away from ignition sources and to dilute spills to non-flammable mixtures. Dike fire control water for appropriate disposal. Solid streams of water may be ineffective and spread material.
For an advanced or massive fire in a large area, use unmanned hose holders or monitor nozzles; if this is not possible withdraw from fire area and allow fire to burn. Withdraw immediately in case of rising sound from venting safety device or any discoloration of tank.
After the fire has been extinguished, toxic atmospheres may remain. Before entering such an area especially confined areas, check the atmosphere with an appropriate monitoring device while wearing full protective suit.
- Protection of Fire Fighters:
- Formaldehyde solutions and its thermal decomposition products are inhalation and skin contact/absorption hazards. Do not enter without wearing specialized protective equipment suitable for the situation. Firefighter's normal protective clothing (Bunker Gear) will not provide adequate protection. A full-body encapsulating chemical protective suit with positive pressure self-contained breathing apparatus (NIOSH approved or equivalent) may be necessary.
|NATIONAL FIRE PROTECTION ASSOCIATION (NFPA) HAZARD IDENTIFICATION
|NFPA - Health:
||3 - Short exposure could cause serious temporary or residual injury. (Formaldehyde solutions; Formaldehyde flammable solutions)
|NFPA - Flammability:
||2 - Must be moderately heated or exposed to relatively high ambient temperatures before ignition can occur. (Formaldehyde solutions)
4 - Will rapidly or completely vaporize at atmospheric pressure and normal ambient temperature, or readily disperse in air and burn readily. (Formaldehyde flammable solutions)
|NFPA - Instability:
||0 - Normally stable, even under fire conditions, and not reactive with water. (Formaldehyde solutions; Formaldehyde flammable solutions)
| SECTION 9. PHYSICAL AND CHEMICAL PROPERTIES
- Conversion Factor:
- 1 ppm = 1.23 mg/m3; 1 mg/m3 = 0.82 ppm at 25 deg C (calculated)
||FREEZING POINT varies with formaldehyde and methanol concentration. -13 to -11 deg C (8.6 to 12.2 deg F) (20% formaldehyde); approximately -16 deg C (3.2 deg F) (25% formaldehyde). Not available for more concentrated formaldehyde solutions or formaldehyde/methanol water solutions.(87)
||Varies with formaldehyde and methanol concentrations. 97.1 deg C (206.8 deg F) (40% formaldehyde, 8-10% methanol); 94.7 deg C (202.5 deg F) (36% formaldehyde, 16% methanol) (84).
|Relative Density (Specific Gravity):
||1.113 (37% formaldehyde) (87); 1.095 (37% formaldehyde, 7% methanol; calculated); 1.080 (37% formaldehyde, 12% methanol; calculated) (1) at 25 deg C (water = 1)
|Solubility in Water:
||Soluble in all proportions.(13)
|Solubility in Other Liquids:
||Soluble in all proportions in alcohols, such as ethanol and methanol, and acetone.(13)
|Coefficient of Oil/Water Distribution (Partition Coefficient):
||Log P(oct) = 0.35 (experimental) (formaldehyde) (85)
||2.5-3.5 (30-55% formaldehyde, 0.5-12% methanol) (7); 2.8-4.0 (37% formaldehyde, 10-15% methanol) (13)
||Water solutions are acidic due to the presence of formic acid, formed by decomposition of formaldehyde in solution.(7,87) Pure formaldehyde solutions are naturally very weakly acidic in the absence of formic acid.(87)
||pKa = 13.4 (Ka = 4 x 10(-14) at 25 deg C (87) (pure formaldehyde solutions)
||5.62 mPa.s (5.62 centipoises) at 25 deg C (37% formaldehyde, 7% methanol) (calculated) (1)
||1.04 (air = 1) (formaldehyde gas)
||PARTIAL PRESSURE OF FORMALDEHYDE: 0.137 kPa (1.025 mm Hg) at 20 deg C (36% formaldehyde) (87,93); 0.173 kPa (1.3 mm Hg) at 20 deg C (37% formaldehyde) (87); the presence of methanol increases the partial pressure of formaldehyde.
|Saturation Vapour Concentration:
||1350-1700 ppm (0.135-0.17%) at 20 deg C (36-37% formaldehyde) (calculated); the presence of methanol will increase the SVC of formaldehyde.
||Not available. The evaporation rate is expected to be low at normal temperatures.
|Henry's Law Constant:
||3.40 x 10(-2) Pa.m3/mol (cited as 3.36 x 10(-7) atm.m3/mol) at 25 deg C (86); log H = -4.86 (dimensionless constant; calculated); also reported as 1.69 x 10(-2) Pa.m3/mol (cited as 1.67 x 10(-7) atm.m3/mol) at 20 deg C (86); log H = -5.16 (dimensionless constant; calculated)
- Other Physical Properties:
- DIELECTRIC CONSTANT: 64 at 20 deg C (30% formaldehyde, 0.1% methanol); 57.6 at 20 deg C (40% formaldehyde, 0.1% methanol) (87)
- Physical Properties Comments:
- The physical properties of formaldehyde solutions depend on the concentration of formaldehyde and other ingredients present in the formulation, (e.g. methanol or other alcohols).
At room temperature or lower, water solutions of monomeric formaldehyde are hydrated to methylene glycol, and partially polymerized to poly(oxymethylene) glycols (e.g. paraformaldehyde). Monomeric formaldehyde is only present in very small concentrations (up to 0.1 wt%).(1,7,87) Formaldehyde can be regenerated from these polymeric forms on heating/and or dilution. Formic acid forms as the temperature increases. The concentrations of formic acid or paraformaldehyde in solution depend on temperature and will increase on standing. Trace metallic impurities, such as iron, can increase the rate of formic acid formation.(1,7)
In formaldehyde/methanol water solutions, formaldehyde and methanol mutually reduce the volatility of each other.(84,87)
Freezing points of formaldehyde solutions with concentration greater than 25% and formaldehyde/methanol water solutions are difficult to measure because polymer precipitation takes place on cooling before the true freezing point is attained. Concentrated solutions solidify due to the precipitation of polymeric hydrates well above 0 deg (32 deg F).(87)
| SECTION 10. STABILITY AND REACTIVITY
- Formaldehyde solutions are unstable and can polymerize at low temperatures unless stabilizers are present. This polymerization reaction is not hazardous. At higher temperatures, formic acid and methanol may form in solutions. Formaldehyde gas can be oxidized slowly in air to produce formic acid.(13)
- Hazardous Polymerization:
- If unstabilized, formaldehyde solutions polymerize to paraformaldehyde. Polymerization is not hazardous.
- Incompatibility - Materials to Avoid:
NOTE: Chemical reactions that could result in a hazardous situation
(e.g. generation of flammable or toxic chemicals, fire or detonation)
are listed here. Many of these reactions can be done safely if
specific control measures (e.g. cooling of the reaction) are in
place. Although not intended to be complete, an overview of
important reactions involving common chemicals is provided to assist
in the development of safe work practices.
STRONG OXIDIZING AGENTS (e.g. hydrogen peroxide, potassium permanganate) - may react violently, with the risk of fire and explosion.(8,9,88)
STRONG BASES (e.g. alkalis, such as sodium hydroxide) - reaction produces flammable hydrogen gas, which may ignite. This reaction may lead to possible pressurization in closed containers, which may rupture.(9)
PHENOL - runaway reactions have occurred during production of phenol-formaldehyde resins.(9)
ACRYLONITRILE - a violently exothermic and runaway reaction may result from the reaction between acrylonitrile and formaldehyde (as paraformaldehyde or trioxane) in the presence of strong acids (e.g. sulfuric acid or acetic anhydride).(9)
PERFORMIC ACID - formaldehyde reacts violently with 90% performic acid.(9)
HYDROCHLORIC ACID - form highly toxic bis(chloromethyl)ether.(8,88)
ANILINE and PERCHLORIC ACID - aniline treated with perchloric acid, then formaldehyde gives a resinous condensation product, which burns with explosive violence.(16)
MAGNESIUM CARBONATE HYDROXIDE - reaction may release carbon dioxide gas, which may rupture closed containers.(9)
UREA, ISOCYANATES, ANHYDRIDES OR OXIDES - may react vigorously or violently.(8)
- Hazardous Decomposition Products:
- Formic acid, methanol
- Conditions to Avoid:
- Open flames, heat, hot surfaces, sparks and other ignition sources.
- Corrosivity to Metals:
- Formaldehyde solutions (37% (formalin) and 50%) are corrosive to 1010 and 1020 carbon steel and gray and ductile cast iron at 20 deg C, due to the presence of formic acid.(87,89,90)
Formaldehyde solutions (37% and 50%) are not corrosive, at 20 deg C, to most common metals, such as stainless steel (such as types 304, 316, 321, 347 and 17-4 pH), type 3003 aluminum, high silicon cast iron, nickel and nickel-base alloys, Monel, Inconel and Incoloy, Carpenter 20Cb-3, naval brass, admiralty brass, naval bronze, tantalum, titanium and zirconium.(89,90)
- Corrosivity to Non-Metals:
- Formaldehyde solutions (37% (formalin) and 50%) attack plastics, such as nylon 6, acrylic fibre (Orlon) and polystyrene (90); and elastomers, such as polyurethane, chloroprene, soft rubber, and isoprene.(89,91,92)
Formaldehyde solutions (37% and 50%) do not attack most plastics, such as Teflon and other fluorocarbons, acrylonitrile-butadiene-styrene (ABS), nylon 66, chlorinated polyvinyl chloride (CPVC), polyvinyl chloride (PVC), polyethylene and polyethylene; and elastomers, such as Viton, Chemraz, Kalrez and other fluorocarbons, ethylene propylene, butyl rubber, nitrile rubber (NBR), neoprene and low density polyethylene.(89,91,92)
| SECTION 11. TOXICOLOGICAL INFORMATION
- LC50 (male mouse): 368 ppm (4-hour exposure); cited as 454 mg/m3 (4-hour exposure; source not specified) (6)
LC50 (rat): 287 ppm (4-hour exposure); cited as 1 mg/L (30-minute exposure; generated from 35.5% solution, methanol content not specified) (25)
- LD50 (oral, guinea pig): 260 mg/kg (cited as 0.26 gm/kg) (administered as a 2% solution; composition not specified) (6)
LD50 (oral, male rat): 800 mg/kg (cited as 0.8 g/kg; administered as a 2% solution; composition not specified) (6)
- LD50 (dermal, rabbit): approximately 300 mg/kg (cited as 270 microL/kg; composition not specified) (2, unconfirmed)
- Eye Irritation:
- Formaldehyde solutions are corrosive to the eyes. Formaldehyde gas is very irritating to the eyes.
- Application of in excess of a 15% solution of a formaldehyde solution (composition not specified) caused severe injury (scored over 5 where 5 is severe injury; graded 8/10).(11) Application of a drop of formalin (formaldehyde and methanol; content not specified) produced very severe eye irritation in rabbits and guinea pigs, with a tendency to recovery in a month or two.(20, unconfirmed)
In a non-standard test, application of a dilute formaldehyde solution (0.05%; composition not specified) to rabbits caused the complete loss of the top cell layer of the eye after a 15-minute application. After 30 minutes the effect was stronger. A more concentrated solution (0.25%) produced very severe damage.(21)
- Skin Irritation:
- Formaldehyde solutions are mild to moderate skin irritants.
- Application of 0.5 mL of a 37% formaldehyde solution (composition not specified), under a patch for 4 hours to intact or broken skin, caused mild to moderate irritation in rabbits (average score 2.8/8).(28) Application of 0.5 mL of a 10% formaldehyde solution (composition not specified), under a patch for 24 hours to intact or broken skin, produced very mild irritation in rabbits (mean scored 0.0-0.5/8; scored at 24 and 48 hours). In a second test, very mild irritation occurred when the application site was covered (average score 0.3/8) and mild irritation was observed when the application site was left open (average score 1.4/8).(22)
- Effects of Short-Term (Acute) Exposure:
- Formaldehyde is a very severe irritant to the upper respiratory tract and eyes. Several studies demonstrate that formaldehyde causes damage to the lining of the nasal cavity in rats exposed to concentrations generally greater than 2-6 ppm.(43)
- Male rats were exposed by whole-body inhalation to 0, 0.7, 2, 6, 10 or 15 ppm formaldehyde (generated by heating paraformaldehyde, 95% purity) for 1, 4 or 9 days (6 hr/d). A dose-dependent increase in lesions in the nasal passages was seen at 10 ppm and higher. There was a significant increase in cell proliferation in the nasal cavity at 6, 10 and 15 ppm for all exposure times.(27)
Similar lesions were observed in the upper respiratory tract of male monkeys exposed to 6 ppm formaldehyde (generated from paraformaldehyde) for 5 days (6 hr/d). Lesions were most severe in the nasal cavity and were minimal in the lower airways. Mild tearing and redness of the eyes was observed during exposures.(26)
In male rats and mice exposed to formaldehyde (generated by heating paraformaldehyde) the 10-minute RD50 (the dose resulting in a decrease in the respiratory rate by 50%) was 4.9 ppm for mice and 31.7 ppm for rats. The RD50 is an indicator of sensory irritation (irritation to the eyes and nose). People exposed to the RD50 would experience intolerable burning of the eyes, nose and throat. Pre-treatment with 2, 6 or 15 ppm formaldehyde for 4 days (6 hr/d) did not significantly affect these values.(23)
Increased airway resistance and hyperreactivity of the lungs has been observed in guinea pigs exposed to low concentrations. Increased airways resistance was observed following exposure to as low as 0.3 ppm formaldehyde (generated from 37% solution, methanol content not specified) for 1 hour.(29) Male guinea pigs were exposed to 0.86, 3.4, 9.4 or 31.1 ppm formaldehyde (generated by heating purified-grade paraformaldehyde) for 2 hours or 0.11, 0.31, 0.59, or 1.05 ppm for 8 hours. Pulmonary resistance and hyperreactivity were significantly increased following exposure to 9.4 ppm for 2 hours, but not to 3.4 ppm or lower. With 8-hour exposures, 1.0 ppm produced pulmonary resistance and hyperreactivity.(30)
Lung injury has been observed at much higher concentrations. A single 6-hour exposure of male rats to 145 ppm formaldehyde (generated from a 20% water solution of formalin; formaldehyde content not specified; 10% methanol) produced severe injury to the nasal cavity, trachea and lungs.(31) Male rats exposed to 128 or 295 ppm formaldehyde (generated from a 12 or 24% water solution of formalin; formaldehyde content not specified; 10% methanol) for 6 hours showed bloody nasal discharge and fluid accumulation in the lungs (pulmonary edema).(32)
Exposure to 15 ppm (cited as 19 mg/m3) formaldehyde (source not specified) for 10 hours caused deaths in guinea pigs (8/20), mice (17/50) and rabbits (3/5). Most deaths occurred after, not during, exposure. Autopsy showed severe lung damage and enlargement of the liver.(24)
- Weanling rats were given formaldehyde (from paraformaldehyde 95% purity, 5% water) in their drinking water at reported doses of 0, 25, or 125 mg/kg/day for 4 weeks. There were no significant differences in growth rate. At 125 mg/kg/day, there was a significant decrease in protein in the urine and in the blood of males and damage to the lining of the stomach in both sexes.(33)
Male rats were orally administered 0, 20, 40 or 80 mg/kg/day formaldehyde (28% in water; methanol content not specified) for 4 weeks. At 80 mg/kg/day, there was a significant decrease in body weight. A dose-related increase in lymph node weights was observed, with significance for relative weight at 20 mg/kg/day. There was also a dose-related decrease in antibody response, which was significant at 40 and 80 mg/kg/day.(34)
- Effects of Long-Term (Chronic) Exposure:
- Several inhalation studies demonstrate that formaldehyde damages the lining of the nasal cavity and the upper respiratory tract in rats exposed to concentrations generally greater than 2 ppm.(4,43,45) Similar lesions were observed in the upper respiratory tracts of male monkeys exposed to 6 ppm formaldehyde (generated from paraformaldehyde) for 6 weeks (6 hr/d, 5 d/wk). Lesions were most severe in the nasal cavity and were minimal in the lower airways. Mild tearing and redness of the eyes was observed during the exposures.(26)
- Male rats were exposed by whole-body inhalation to 0, 0.7, 2, 6, 10 or 15 ppm formaldehyde (generated by heating paraformaldehyde, 95% purity) for 6 weeks (6 hr/d, 5 d/wk). A dose-dependent increase in lesions in the nasal passages was seen at 6 ppm and higher. There was a significant increase in cell proliferation in the nasal cavity at 6 ppm and higher.(27)
Rats were exposed to 0, 1, 10 or 20 ppm formaldehyde (generated by heating paraformaldehyde, 97-99% purity) for 13 weeks (6 hr/d, 5 d/wk). At 20 ppm, there were uncoordinated movements during the first 30 minutes of each exposure and a significant decrease in body weight. There were also significant increases in plasma enzymes, which may have indicated liver effects or may have resulted from the decreased growth. At 10 and 20 ppm, there was dose-related damage to the lining of the nasal cavity.(35)
Male rats were exposed to 0, 0.1, 1.0 or 10 ppm formaldehyde (generated by heating paraformaldehyde, 97-99% purity) for 13 or 52 weeks (6 hr/d, 5 d/wk). A significant decrease in body weight gain was seen at 10 ppm, starting after 2 weeks exposure. Severe damage to the nasal passages was noted at 10 ppm, but not at 1 ppm, for both 13- and 52-week exposures.(35)
Mice were exposed to 0, 2, 4, 10, 20 or 40 ppm formaldehyde (generated from a 9.2% water solution of formaldehyde) for 13 weeks (6 hr/d, 5 d/wk). At 20 and 40 ppm there was a marked loss of body weight (significance not reported), and signs of laboured breathing, listlessness, hunched posture and loss of coordination. Harmful effects on the nasal cavity were seen at 10 ppm and higher. Damage to the trachea and larynx were seen at 20 and 40 ppm and lung lesions were noted in some animals at 40 ppm.(77)
- Skin Contact:
- Hairless mice received skin applications (uncovered) of 200 microL of 1 or 10% formaldehyde in water (made from formalin with 40% formaldehyde, methanol content not specified) twice a week for 60 weeks. The higher dose group showed skin swelling and ulcers. The lower dose group showed no skin effects.(37)
- Rats were given formaldehyde (from paraformaldehyde 95% purity, 5% water) in their drinking water for up to 2 years. Reported doses were 0, 1.2, 15 or 82 mg/kg/day for males, and 0, 1.8, 21 or 109 mg/kg/day for females. At 82 or 109 mg/kg/day, there were changes in growth rates, in urine chemistry and in the kidneys. However, these effects were probably caused by a 40% decrease in water intake. Irritant damage to the lining of the stomach was seen in males at 82 mg/kg/day and in females at 109 mg/kg/day.(38)
Rats were given formaldehyde (water solutions made from crystalline paraformaldehyde, 80% purity) in their drinking water at concentrations of 0, 0.02, 0.10 or 0.50% for 2 years. Reported estimated doses were 0, 10, 50 or 300 mg/kg/day. At 300 mg/kg/day, there was a significant increase in mortality and a significant decrease in body weight gain. Irritant damage to the lining of the stomach was seen at 300 mg/kg/day and to a lesser extent at 50 mg/kg/day.(39)
- Skin Sensitization:
- Studies with guinea pigs and mice prove that formaldehyde solutions cause skin sensitization.
- Positive results were obtained in mice using the Local Lymph Node Assay.(40) In a Magnusson-Kligman test, with an adjuvant, positive results were obtained in 9/10 guinea pigs induced with 2 intradermal injections and 7/10 guinea pigs induced with 4 intradermal injections.(42)
- The International Agency for Research on Cancer (IARC) has determined that there is sufficient evidence of the carcinogenicity of formaldehyde in animals.(19)
- Animal studies on the carcinogenicity of formaldehyde have been extensively reviewed elsewhere.(3,5,19,43,44,45)
Formaldehyde has been tested for carcinogenicity by inhalation in mice, rats and hamsters, by ingestion in rats, by skin application in mice, and by subcutaneous injection in rats and hamsters. In rat inhalation studies, there was an increase in squamous cell carcinomas in the nasal cavity at exposure levels of 5.6 ppm and higher. The concentrations of formaldehyde that cause nasal tumours also cause degeneration, inflammation, and tissue death (necrosis) of the lining of the nasal cavity. It is believed that these changes play a role in the induction of the tumours.(36) Similar effects were not observed in hamsters. Studies in mice either showed no effect or were inadequate for evaluation.(19) In rats receiving formaldehyde in drinking water, tumours in the digestive tract and/or leukemia were caused in 2/4 studies. The studies with skin or subcutaneous exposure are considered inadequate for evaluation.(19)
- Teratogenicity, Embryotoxicity and/or Fetotoxicity:
- The available evidence does not indicate that formaldehyde is a developmental toxin. Numerous studies have evaluated the potential developmental toxicity of formaldehyde with inhalation, ingestion or skin contact with rats, mice, rabbits and beagle dogs.(43,44,46,47,48) Many of the studies have design limitations, such as low animal numbers, lack of detailed information on methods, and lack of information on maternal toxicity. Well-conducted studies do not show fetal effects in the absence of maternal toxicity.
- Rats were exposed by inhalation to 2, 5, or 10 ppm formaldehyde (source not specified) from days 6-15 of pregnancy (6 hr/d). No maternal or fetal deaths occurred. At 10 ppm, there was significantly decreased food consumption and weight gain in the mothers, but no evidence of any developmental effects.(50)
Rats were exposed by inhalation to 0, 5, 10, 20 or 40 ppm formaldehyde (generated from 37% water solution of formaldehyde with 10% methanol) from days 6-20 of pregnancy (6 hr/d). There was a decrease in body weight gain in mothers, which was slight at 20 ppm and significant at 40 ppm. No significant effects were observed on implantation, fetal loss, resorptions or the number of live fetuses/litter. There was a dose-related decrease in fetal body weight, which was significant at 40 ppm for females and at 20 ppm for males. There were no significant increases in skeletal or soft tissue malformations. A methanol control was not included in this study.(49) This study suggests that slight fetotoxicity (slightly reduced fetal weight) may occur in the absence of maternal toxicity at 20 ppm formaldehyde, but the presence of methanol, which is fetotoxic and teratogenic, may have influenced the results. Teratogenic and embryotoxic effects were not observed, even with the presence of methanol.
- Reproductive Toxicity:
- The few limited reproductive toxicity studies available are reviewed elsewhere.(43,44,46,47) Limitations include the use of a small number of animals and only one exposure group, as well as the fact that exposures were mostly to chemicals that release formaldehyde in the body, rather than formaldehyde itself. However, in general, these studies suggest that formaldehyde exposure will not affect fertility.
- In one study, male rats were orally given 100 or 200 mg/kg formaldehyde (40% solution in water, 11-14% methanol) and killed 11 days following exposure. There was no difference in testes weight at either dose. At 200 mg/kg, there was a significant increase in sperm counts and in the percentage of abnormal sperm heads compared to controls.(51) There was no methanol control group, and no assessment of the effect on fertility.
- Formaldehyde is considered mutagenic, based on a positive result (chromosomal aberrations in lung cells) observed in male rats exposed by inhalation to 95% pure formaldehyde. A positive result (DNA-protein crosslinks) was also obtained in rats exposed by inhalation to 95% pure formaldehyde. Positive results were obtained in most studies using cultured mammalian cells, mostly without metabolic activation. Both positive and negative results were obtained in bacteria. Positive results for a wide range of genetic tests were obtained in studies using fruit flies.
- The numerous in vivo studies available for formaldehyde are reviewed elsewhere.(19,43,44,56) Many studies involved exposure to formaldehyde with methanol as a stabilizer, or the purity of the formaldehyde was not specified. In some cases, the route of exposure used was not relevant to occupational exposures (e.g. intraperitoneal injection). The following studies are well conducted, with exposures to relatively pure formaldehyde. These studies demonstrate that formaldehyde is mutagenic to the somatic cells of live animals. There is insufficient information available to conclude that formaldehyde is mutagenic to germs cells.
The induction of chromosomal aberrations in bone marrow and lung cells was studied in male rats exposed by whole-body inhalation to 0, 0.5, 3.0 or 15 ppm formaldehyde (generated by heating paraformaldehyde; 95% purity) for 1 or 8 weeks (6 hr/d, 5 d/wk). Negative results were obtained for bone marrow. Positive results were obtained for lung cells (a dose-related increase after 1 and 8 week exposures, with statistical significance at 15 ppm).(52)
A positive result (DNA-protein crosslinks) was obtained in rats exposed by whole-body inhalation to 0, 0.7, 2,6 or 15 ppm formaldehyde (generated by heating paraformaldehyde, 95% purity) for 12 weeks (6 hr/d, 5 d/wk). There was a dose-related increase in DNA-protein crosslinks in nasal mucosal cells, which was significant at 6 ppm.(53)
A positive result (micronucleus induction in cells of the digestive tract) was obtained in male rats given an oral dose of 200 mg/kg formaldehyde (composition not specified) dissolved in water. The response increased with time and reached a maximum at 30 hours following exposure.(55)
Male mice dosed orally with 4, 10, 25, 50 or 100 mg/kg radio-labelled (C14) formaldehyde (98% purity) had a significant linear dose-related increase in sperm head alkylation, but the authors did not measure direct effect on DNA.(54) Positive results (sperm shape abnormality, chromosome aberrations, bone marrow micronucleus) have also been obtained in studies using formaldehyde with methanol present or purity not specified.
- Positive results (gene mutation, DNA damage, DNA repair, sister chromatid exchanges, chromosome aberrations) were obtained in many tests using cultured human and other mammalian cells. Most tests were done without metabolic activation.(19,43,46,56) Both positive and negative (gene mutation) results were obtained in bacteria, with and without metabolic activation. In general, the presence of metabolic activation decreased the mutagenic activity.(5,19,46,56) Positive results were also obtained in tests using yeast.(19,46,56) The purity of the formaldehyde and presence of methanol was not addressed in the reviews of these studies. However, even in studies where methanol is present, the positive findings are believed to be caused by formaldehyde.
- Most studies with fruit flies (Drosophila) have shown positive results for a wide range of genetic tests.(5,19,56) The purity of the formaldehyde and presence of methanol was not addressed in the reviews of these studies.
- Toxicological Synergisms:
- Several studies have exposed animals to formaldehyde in combination with other carcinogens. In some of these studies, formaldehyde enhanced the effect of the other carcinogens, causing more tumours or faster tumour growth.(19) In two studies, inhalation exposure to formaldehyde significantly enhance respiratory sensitization to a known allergen (ovalbumin) in guinea pigs and mice.(57,58)
| SECTION 16. OTHER INFORMATION
- Selected Bibliography:
- (1) Gerberich, H.R., et al. Formaldehyde. In: Kirk-Othmer encyclopedia of chemical technology. 4th ed. Vol. 11. John Wiley and Sons, 1994. p. 929-951
(2) National Institute for Occupational Safety and Health (NIOSH). Formaldehyde. Last updated: 2003-05. In: Registry of Toxic Effects of Chemical Substances (RTECS(R)). [CD-ROM]. Canadian Centre for Occupational Health and Safety (CCOHS). Also available at: <www.ccinfoweb.ccohs.ca/rtecs/search.html>
(3) International Agency for Research on Cancer (IARC). Formaldehyde. In: IARC monographs on the evaluation of carcinogenic risks to humans. Vol. 29. Some industrial chemicals and dyestuffs. World Health Organization, 1982. p. 345-389
(4) Formaldehyde. In: Documentation of threshold limit values and biological exposure indices. 7th ed. American Conference of Governmental Industrial Hygienists, 2001
(5) Fielder, R.J., et al. Toxicity review 2 : Formaldehyde. Health and Safety Executive, 1981. p. 1-18
(6) Safronov, G.A., et al. Comparative acute inhalation toxicity of aliphatic aldehydes and ketones according to exposure time. Current Toxicology. Vol. 1, no. 1 (1993). p. 47-51
(7) Reuss, G., et al. Formaldehyde. In: Ullmann's encyclopedia of industrial chemistry. 5th completely revised ed. Vol. A 11. VCH Publishers, 1988. p. 619-651
(8) Formalin (as formaldehyde) In: NIOSH pocket guide to chemical hazards. National Institute for Occupational Safety and Health, June 1997. p. 148-149
(9) Urben, P.G., ed. Bretherick's reactive chemical hazards database. [CD-ROM]. 6th ed. Version 3.0. Butterworth-Heinemann Ltd., 1999
(10) Smyth, Jr., H.F., et al. The single dose toxicity of some glycols and derivatives. Journal of Industrial Hygiene and Toxicology. Vol. 23, no. 6 (1941). p. 259-268
(11) Carpenter, C.P., et al. Chemical burns of the rabbit cornea. American Journal of Ophthalmology. Vol. 29 (1946). p. 1363-1372
(12) Odor thresholds for chemicals with established occupational health standards. American Industrial Hygiene Association, 1989. p. 20, 60
(13) Formaldehyde solutions. The Merck index: an encyclopedia of chemicals, drugs and biologicals. Edited by M.J. O'Neil, et al. 13th ed. Merck and Company, 2001. p. 751
(14) Report on Carcinogens. 11th ed. US Department of Health and Human Services, Public Health Service, National Toxicology Program
(15) Forsberg, K., et al. Quick selection guide to chemical protective clothing. 4th ed. Van Nostrand Reinhold, 2002
(16) Fire protection guide to hazardous materials. 13th ed. Edited by A.B. Spencer, et al. National Fire Protection Association, 2002. NFPA 49; NFPA 325; NFPA 491
(17) International Agency for Research on Cancer (IARC). IARC classifies formaldehyde as carcinogenic to humans. Press Release No. 153. World Health Organization, June 15, 2004. Available at: <www.iarc.fr/pageroot/PRELEASES/pr153a.html>
(18) European Communities. Commission Directive 96/54/EC. July 30, 1996
(19) International Agency for Research on Cancer (IARC). Formaldehyde. In: IARC monographs on the evaluation of carcinogenic risks to humans. Vol. 62. Wood dust and formaldehyde. World Health Organization, 1995. p. 217-362
(20) Grant, W.M., et al. Toxicology of the Eye. 4th ed. Charles C. Thomas, 1993. p. 708-714
(21) Dormans, J.A.M.A., et al. The effect of ophthalmic preservatives on corneal epithelium of the rabbit: A scanning electron microscopical study. Toxicology and Applied Pharmacology. Vol. 62, no. 2 (Feb. 1982). p. 251-261
(22) Steinberg, M., et al. A comparison of test techniques based on the rabbit and human skin response to irritants with recommendations regarding the evaluation of mildly or moderately irritating compounds. In: Animal Models in Dermatology. Edited by H.I. Maibach. Churchill Livingston, 1975. p. 1-11
(23) Chang, J.C.F., et al. Effect of single or repeated formaldehyde exposure on minute volume of B6C3F1 mice and F-344 rats. Toxicology and Applied Pharmacology. Vol. 61, no. 3 (1981). p. 451-459
(24) Salem, H., et al. Inhalation toxicities of some aldehydes. Toxicology and Applied Pharmacology. Vol. 2, no. 2 (1960). p. 183-187
(25) Skog, E. A toxicological investigation of lower aliphatic aldehydes. I. Toxicity of formaldehyde, acetaldehyde, propionaldehyde and butyraldehyde; as well as of acrolein and crotonaldehyde. Acta Pharmacol. Vol. 6 (1950). p. 299-318
(26) Monticello, T.M., et al. Effects of formaldehyde gas on the respiratory tract of Rhesus monkeys, pathology and cell proliferation. American Journal of Pathology. Vol. 134, no. 3 (Mar. 1989). p. 515-527
(27) Monticello, T.M., et al. Regional increases in rat nasal epithelial cell proliferation following acute and subchronic inhalation of formaldehyde. Toxicology and Applied Pharmacology. Vol. 111 (1991). p. 409-421
(28) Industrial Biotest Labs Inc. Primary skin irritation tests with 18 chemicals in albino rabbits. Celanese Chemical Company Inc. Date produced: July 28, 1972. EPA/OTS 878212151. NTIS/OTS84003A.
(29) Amdur, M.O. The response of guinea pigs to inhalation of formaldehyde and formic acid alone and with a sodium chloride aerosol. International Journal of Air Pollution. Vol. 3, no. 4 (1960). p. 201-220
(30) Swiecichowski, A.L., et al. Formaldehyde-induced airway hyperreactivity in vivo and ex vivo in guinea pigs. Environmental Research. Vol. 61, no, 2 (1993). p. 185-199
(31) Kamata, E., et al. Effects of formaldehyde vapor on the nasal cavity and lungs of F-344 rats. Journal of Environmental Pathology, Toxicology and Oncology. Vol. 15, no. 1 (1996). p. 1-8
(32) Kamata, E., et al. Acute inhalation toxicity study of formaldehyde in rats: effect of vapor on the pulmonary surfactant. Pharmacometrics. Vol. 51, no. 1 (1996). p. 33-37
(33) Til, H.P., et al. Evaluation of the oral toxicity of acetaldehyde and formaldehyde in a 4 week drinking water study in rats. Food and Chemical Toxicology. Vol. 26, no. 5 (1988). p. 447-452
(34) Vargova, M., et al. Subacute immunotoxicity study of formaldehyde in male rats. Drug and Chemical Toxicology. Vol. 16, no. 3 (1993). p. 255-275
(35) Woutersen, R.A., et al. Subchronic (13-week) inhalation toxicity study of formaldehyde in rats. Journal of Applied Toxicology. Vol. 71, no. 1 (1987). p. 43-49
(36) Appelman, L.M., et al. One-year inhalation toxicity study of formaldehyde in male rats with a damage or undamaged nasal mucosa. Journal of Applied Toxicology. Vol. 8, no. 2 (1988). p. 85-90
(37) Iverson, O.H. Formaldehyde and skin carcinogenesis. Environment International. Vol. 12 (1986). p. 541-544
(38) Til, H.P., et al. Two year drinking water study of formaldehyde in rats. Food and Chemical Toxicology. Vol. 27, no. 2 (Feb. 1989). p. 77-87
(39) Tobe, M., et al. Chronic toxicity study on formaldehyde administered orally to rats. Toxicology. Vol. 56 (1989). p. 79-86
(40) Basketter, D.A., et al. Comparison of the Local Lymph Node Assay with the Guinea Pig Maximization Test for the detection of a range of contact allergens. Food and Chemical Toxicology. Vol. 30, no. 1 (1992). p. 65-69
(41) Maibach, H. Formaldehyde: effects on animal and human skin. In: Formaldehyde toxicity. Edited by J.E. Gibson. Hemisphere Publishing Corp., 1983. p. 166-174
(42) Maurer, T., et al. The maximization test for skin sensitization potential - updating the standard protocol and validation of a modified protocol. Food and Chemical Toxicology. Vol. 27, no. 12 (1989). p. 807-811
(43) Agency for Toxic Substances and Disease Registry. Toxicological profile for formaldehyde. Public Health Service, US Department of Health and Human Services, July 1999
(44) International Programme on Chemical Safety (IPCS). Formaldehyde. Environmental Health Criteria 89. World Health Organization, 1989
(45) International Programme on Chemical Safety. Formaldehyde. Concise International Chemical Assessment Document (CICAD) 40. World Health Organization, 2002
(46) Feinman, S.E. Formaldehyde genotoxicity and teratogenicity. In: Formaldehyde Sensitivity and Toxicity. Edited by S.E. Feinman. CRC Press, 1988. p. 167-178
(47) Collins, J.J., et al. A review of adverse pregnancy outcomes and formaldehyde exposure in human and animal studies. Regulatory Toxicology and Pharmacology. Vol. 34 (2001). p. 17-34
(48) Thrasher, J.D., et al. Embryotoxicity and teratogenicity of formaldehyde. Archives of Environmental Health. Vol. 56, no. 4 (July/Aug. 2001). p. 300-311
(49) Saillenfait, A.M. The effects of maternally inhaled formaldehyde on embryonal and foetal development in rats. Food and Chemical Toxicology. Vol. 27, no. 8 (1989). p. 545-548
(50) Martin, W.J. A teratology study of inhaled formaldehyde in the rat. Reproductive Toxicology. Vol. 4, no. 3 (1990). p. 237-239
(51) Cassidy, S.L., et al. Evaluation of a testicular sperm head counting technique using rats exposed to dimethoxyethyl phthalate (DMEP), glycerol a-monochlorohydrin (GMCH), epichlorohydrin (ECH), formaldehyde (FA), or methylmethanesulfonate (MMS). Archives of Toxicology. Vol. 53 (1983). p. 71-78
(52) Dallas, C.E., et al. Cytogenetic analysis of pulmonary lavage and bone marrow cells of rats after repeated formaldehyde inhalation. Journal of Applied Toxicology. Vol. 12, no. 3 (1992). p. 199-203
(53) Casanova, M., et al. DNA-protein cross-links and cell replication at specific sites in the nose of F344 rats exposed subchronically to formaldehyde. Fundamental and Applied Toxicology. Vol. 23 (1994). p. 525-536
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- Information on chemicals reviewed in the CHEMINFO database is drawn from a number of publicly available sources. A list of general references used to compile CHEMINFO records is available in the database Help.
|Review/Preparation Date: 2004-07-08
- Revision Indicators:
|WHMIS proposed classification
|WHMIS classification comments
|WHMIS detailed classification