METHYLAMINE
HAZARDTEXT ®
Information to help in the initial response for evaluating chemical incidents
-IDENTIFICATION
SYNONYMS
AMINOMETHANE ANHYDROUS METHYLAMINE CARBINAMINE MERCURIALIN METHANAMINE METHYLAMINE METHYLAMINE, ANHYDROUS METHYLAMINE, AQUEOUS SOLUTION METHYLAMINEN (Dutch) METILAMINE (Italian) METYLOAMINA (Polish) MMA MONOMETHYLAMINE MONOMETHYLAMINE, ANHYDROUS
IDENTIFIERS
1061-Methylamine, anhydrous 1235-Methylamine, aqueous solution
SYNONYM REFERENCE
- (HSDB , 1999; RTECS , 1999)
USES/FORMS/SOURCES
Methylamine is used in the tanning and dying industries, as a fuel additive, as an intermediate in the production of pharmaceuticals, agricultural chemicals, rubber chemicals, surfactants, explosives, and accelerators, as a polymerization inhibitor, and as a component of paint removers, solvents, photographic developers and rocket propellant (ACGIH, 1991; Budavari, 1996; CGA, 1990; Hathaway et al, 1996; Lewis, 1997).
Methylamine is available as a compressed gas and as a 30%-50% aqueous solution. Anhydrous methylamine is available in grades of 98% purity and above. (ACGIH, 1991; Ashford, 1994; CGA, 1990; Lewis, 1997).
-CLINICAL EFFECTS
GENERAL CLINICAL EFFECTS
- Methylamine is a moderate to severe irritant of the eyes, skin, and respiratory tract. Corneal damage may occur with direct eye contact.
Coughing, nausea, and pulmonary edema may occur following inhalation. Olfactory fatigue occurs rapidly with inhalation exposure.
- Chemical or allergic bronchitis has followed inhalation exposure to methylamine. Contact with the liquid may cause frostbite.
- Methylamine has not been associated with long-term effects, systemic adverse effects, or dermal sensitization in humans. Hepatotoxicity has been seen in experimental animals.
- Mutation data exists for methylamine. No carcinogenicity data were available for methylamine at the time of this review.
- POTENTIAL HEALTH HAZARDS - EMERGENCY RESPONSE GUIDEBOOK, GUIDE 118 (ERG, 2004)
May cause toxic effects if inhaled. Vapors are extremely irritating. Contact with gas or liquefied gas may cause burns, severe injury and/or frostbite. Fire will produce irritating, corrosive and/or toxic gases. Runoff from fire control may cause pollution.
- POTENTIAL HEALTH HAZARDS - EMERGENCY RESPONSE GUIDEBOOK, GUIDE 132 (ERG, 2004)
May cause toxic effects if inhaled or ingested/swallowed. Contact with substance may cause severe burns to skin and eyes. Fire will produce irritating, corrosive and/or toxic gases. Vapors may cause dizziness or suffocation. Runoff from fire control or dilution water may cause pollution.
-MEDICAL TREATMENT
LIFE SUPPORT
- Support respiratory and cardiovascular function.
SUMMARY
- FIRST AID - EMERGENCY RESPONSE GUIDEBOOK, GUIDE 118 (ERG, 2004)
Move victim to fresh air. Call 911 or emergency medical service. Give artificial respiration if victim is not breathing. Do not use mouth-to-mouth method if victim ingested or inhaled the substance; give artificial respiration with the aid of a pocket mask equipped with a one-way valve or other proper respiratory medical device. Administer oxygen if breathing is difficult. Remove and isolate contaminated clothing and shoes. In case of contact with liquefied gas, thaw frosted parts with lukewarm water. In case of burns, immediately cool affected skin for as long as possible with cold water. Do not remove clothing if adhering to skin. Keep victim warm and quiet. Keep victim under observation. Effects of contact or inhalation may be delayed. Ensure that medical personnel are aware of the material(s) involved and take precautions to protect themselves.
- FIRST AID - EMERGENCY RESPONSE GUIDEBOOK, GUIDE 132 (ERG, 2004)
Move victim to fresh air. Call 911 or emergency medical service. Give artificial respiration if victim is not breathing. Do not use mouth-to-mouth method if victim ingested or inhaled the substance; give artificial respiration with the aid of a pocket mask equipped with a one-way valve or other proper respiratory medical device. Administer oxygen if breathing is difficult. Remove and isolate contaminated clothing and shoes. In case of contact with substance, immediately flush skin or eyes with running water for at least 20 minutes. In case of burns, immediately cool affected skin for as long as possible with cold water. Do not remove clothing if adhering to skin. Keep victim warm and quiet. Effects of exposure (inhalation, ingestion or skin contact) to substance may be delayed. Ensure that medical personnel are aware of the material(s) involved and take precautions to protect themselves.
FIRST AID EYE EXPOSURE - If solution containing the contaminant contacts the eyes, immediately wash the eyes with large amounts of water, occasionally lifting the lower and upper lids. Get medical attention immediately. Contact lenses should not be worn when working with this chemical. If eye tissue is frozen, seek medical attention immediately; if tissue is not frozen, immediately and thoroughly flush the eyes with large amounts of water for at least 15 minutes. If irritation, pain, swelling, lacrimation, or photophobia persist, get medical attention as soon as possible.
DERMAL EXPOSURE - If solution containing the contaminant contacts the skin, immediately flush the contaminated skin with water. If this chemical penetrates the clothing, immediately remove the clothing and flush the skin with water. Get medical attention promptly. If frostbite has occurred, seek medical attention immediately; do NOT rub the affected areas or flush them with water. In order to prevent further tissue damage, do NOT attempt to remove frozen clothing from frostbitten areas. If frostbite has NOT occurred, immediately and thoroughly wash contaminated skin with soap and water.
INHALATION EXPOSURE - Move the exposed person to fresh air at once. If breathing has stopped, perform artificial respiration. Keep the affected person warm and at rest. Get medical attention as soon as possible. ORAL EXPOSURE - If solution containing the contaminant has been swallowed, get medical attention as soon as possible. TARGET ORGANS - Eyes, skin, and respiratory system (National Institute for Occupational Safety and Health, 2007).
GENERAL - Move victims of inhalation exposure from the toxic environment and administer 100% humidified supplemental oxygen with assisted ventilation as required. Exposed skin and eyes should be copiously flushed with water. Ingestion may result in significant esophageal or gastrointestinal tract irritation or burns, and EMESIS SHOULD NOT BE INDUCED. Cautious gastric lavage followed by administration of activated charcoal may be of benefit if the patient is seen soon after the exposure.
INHALATION EXPOSURE - INHALATION: Move patient to fresh air. Monitor for respiratory distress. If cough or difficulty breathing develops, evaluate for respiratory tract irritation, bronchitis, or pneumonitis. Administer oxygen and assist ventilation as required. Treat bronchospasm with an inhaled beta2-adrenergic agonist. Consider systemic corticosteroids in patients with significant bronchospasm. If bronchospasm and wheezing occur, consider treatment with inhaled sympathomimetic agents. ACUTE LUNG INJURY: Maintain ventilation and oxygenation and evaluate with frequent arterial blood gases and/or pulse oximetry monitoring. Early use of PEEP and mechanical ventilation may be needed. This agent may cause hepatotoxicity. Monitor liver function tests in patients with significant exposure.
DERMAL EXPOSURE - DECONTAMINATION: Remove contaminated clothing and jewelry and irrigate exposed areas with copious amounts of water. A physician may need to examine the area if irritation or pain persists. Treat dermal irritation or burns with standard topical therapy. Patients developing dermal hypersensitivity reactions may require treatment with systemic or topical corticosteroids or antihistamines.
EYE EXPOSURE - DECONTAMINATION: Remove contact lenses and irrigate exposed eyes with copious amounts of room temperature 0.9% saline or water for at least 15 minutes. If irritation, pain, swelling, lacrimation, or photophobia persist after 15 minutes of irrigation, the patient should be seen in a healthcare facility.
INGESTION EXPOSURE - Because of the potential for severe gastrointestinal tract irritation or burns, do not induce emesis. Significant esophageal or gastrointestinal tract irritation or burns may occur following ingestion. The possible benefit of early removal of some ingested material by cautious gastric lavage must be weighed against potential complications of bleeding or perforation. GASTRIC LAVAGE: Consider after ingestion of a potentially life-threatening amount of poison if it can be performed soon after ingestion (generally within 1 hour). Protect airway by placement in the head down left lateral decubitus position or by endotracheal intubation. Control any seizures first. ACTIVATED CHARCOAL: Administer charcoal as a slurry (240 mL water/30 g charcoal). Usual dose: 25 to 100 g in adults/adolescents, 25 to 50 g in children (1 to 12 years), and 1 g/kg in infants less than 1 year old. Observe patients with ingestion carefully for the possible development of esophageal or gastrointestinal tract irritation or burns. If signs or symptoms of esophageal irritation or burns are present, consider endoscopy to determine the extent of injury.
-RANGE OF TOXICITY
MINIMUM LETHAL EXPOSURE
The approximate oral LD50 for rats given a 40% amine base solution of methylamine ranges from 100 to 200 mg/kg body weight. When given the hydrochloride salt of methylamine, the approximate oral LD50 for rats ranges from 1600 to 3200 mg/kg body weight (ACGIH, 1991). "Five rats given three, daily, oral doses of 200 mg/kg methylamine died within 5 days" (ACGIH, 1991).
MAXIMUM TOLERATED EXPOSURE
Methylamine is a severe irritant of the eyes and skin; brief exposures to 20-100 ppm produce transient eye, nose, and throat irritation. Exposure to higher concentrations or a liquid splash of methylamine may be as damaging to the eye as ammonia. Inhalation of higher concentrations results in violent sneezing, a burning sensation of the throat with laryngeal constriction, difficulty in breathing with chest congestion, eye inflammation, and may cause pulmonary edema. Skin contact with methylamine causes dermatitis. There were no accounts of long-term effects, systemic reactions, or skin sensitization found in the literature (ACGIH, 1991; CGA, 1990; Clayton & Clayton, 1994; Grant, 1993; Hathaway et al, 1996; Harbison, 1998; Snyder et al, 1990).
Necrosis occurred after 0.1 mL of a 40% aqueous solution of methylamine was applied to the skin of a guinea pig. Hemorrage and necrosis also occurred after an application of liquified methylamine to the skin of guinea pig (ACGIH, 1991). One drop of a 40% aqueous solution of methylamine base caused immediate and severe irritation to the eye of a rabbit. One drop of a 40% aqueous solution of methylamine hydrochloride caused only mild irritation to a rabbit's eye, which returned to normal within 24 hours (ACGIH, 1991). "In another study with rabbits, a 5% aqueous solution of methylamine was reported to cause conjunctival hemorrhage, superficial corneal opacities, and edema" (ACGIH, 1991).
- Carcinogenicity Ratings for CAS74-89-5 :
ACGIH (American Conference of Governmental Industrial Hygienists, 2010): Not Listed ; Listed as: Methylamine EPA (U.S. Environmental Protection Agency, 2011): Not Listed IARC (International Agency for Research on Cancer (IARC), 2016; International Agency for Research on Cancer, 2015; IARC Working Group on the Evaluation of Carcinogenic Risks to Humans, 2010; IARC Working Group on the Evaluation of Carcinogenic Risks to Humans, 2010a; IARC Working Group on the Evaluation of Carcinogenic Risks to Humans, 2008; IARC Working Group on the Evaluation of Carcinogenic Risks to Humans, 2007; IARC Working Group on the Evaluation of Carcinogenic Risks to Humans, 2006; IARC, 2004): Not Listed NIOSH (National Institute for Occupational Safety and Health, 2007): Not Listed ; Listed as: Methylamine MAK (DFG, 2002): Not Listed NTP (U.S. Department of Health and Human Services, Public Health Service, National Toxicology Project ): Not Listed
TOXICITY AND RISK ASSESSMENT VALUES
- EPA Risk Assessment Values for CAS74-89-5 (U.S. Environmental Protection Agency, 2011):
CALCULATIONS
1 mg/L = 783 ppm (Clayton & Clayton, 1994) 1 ppm = 1.27 mg/m(3) (Clayton & Clayton, 1994)
-STANDARDS AND LABELS
WORKPLACE STANDARDS
- ACGIH TLV Values for CAS74-89-5 (American Conference of Governmental Industrial Hygienists, 2010):
Editor's Note: The listed values are recommendations or guidelines developed by ACGIH(R) to assist in the control of health hazards. They should only be used, interpreted and applied by individuals trained in industrial hygiene. Before applying these values, it is imperative to read the introduction to each section in the current TLVs(R) and BEI(R) Book and become familiar with the constraints and limitations to their use. Always consult the Documentation of the TLVs(R) and BEIs(R) before applying these recommendations and guidelines.
- AIHA WEEL Values for CAS74-89-5 (AIHA, 2006):
- NIOSH REL and IDLH Values for CAS74-89-5 (National Institute for Occupational Safety and Health, 2007):
Listed as: Methylamine REL: IDLH: IDLH: 100 ppm Note(s): Not Listed
- OSHA PEL Values for CAS74-89-5 (U.S. Occupational Safety, and Health Administration (OSHA), 2010):
- OSHA List of Highly Hazardous Chemicals, Toxics, and Reactives for CAS74-89-5 (U.S. Occupational Safety and Health Administration, 2010):
ENVIRONMENTAL STANDARDS
- EPA CERCLA, Hazardous Substances and Reportable Quantities for CAS74-89-5 (U.S. Environmental Protection Agency, 2010):
- EPA CERCLA, Hazardous Substances and Reportable Quantities, Radionuclides for CAS74-89-5 (U.S. Environmental Protection Agency, 2010):
- EPA RCRA Hazardous Waste Number for CAS74-89-5 (U.S. Environmental Protection Agency, 2010b):
- EPA SARA Title III, Extremely Hazardous Substance List for CAS74-89-5 (U.S. Environmental Protection Agency, 2010):
- EPA SARA Title III, Community Right-to-Know for CAS74-89-5 (40 CFR 372.65, 2006; 40 CFR 372.28, 2006):
- DOT List of Marine Pollutants for CAS74-89-5 (49 CFR 172.101 - App. B, 2005):
- EPA TSCA Inventory for CAS74-89-5 (EPA, 2005):
SHIPPING REGULATIONS
- DOT -- Table of Hazardous Materials and Special Provisions for UN/NA Number 1061 (49 CFR 172.101, 2005):
- DOT -- Table of Hazardous Materials and Special Provisions for UN/NA Number 1235 (49 CFR 172.101, 2005):
- ICAO International Shipping Name for UN1061 (ICAO, 2002):
- ICAO International Shipping Name for UN1235 (ICAO, 2002):
LABELS
- NFPA Hazard Ratings for CAS74-89-5 (NFPA, 2002):
Listed as: Methylamine Hazard Ratings: Health Rating (Blue): 3 (3) Seriously toxic material. Short term exposure could cause serious temporary or residual injury even though prompt medical treatment is given. Includes known or suspect small animal carcinogens, mutagens, or teratogens.
Flammability Rating (Red): 4 (4) Extremely flammable. Materials which will rapidly vaporize at normal pressure and temperature and will burn readily. Including: gases, cryogenic materials, any liquid or gaseous material having a flash point below 73 degrees F and a boiling point below 100 degrees F, and materials which can form explosive mixtures with air.
Instability Rating (Yellow): 0 Oxidizer/Water-Reactive Designation: Not Listed
-HANDLING AND STORAGE
SUMMARY
Methylamine is moderately toxic by inhalation and is a severe skin irritant. Wear appropriate protective clothing to prevent any possibility of skin contact. Wash immediately if skin becomes wet or contaminated; remove clothing immediately if it becomes wet or contaminated to avoid fire hazard. Methylamine is a very dangerous fire hazard when exposed to heat or flame. Sources of ignition are prohibited wherever methylamine is handled, used, or stored. Use only non-sparking tools and equipment, especially when opening and closing containers of methylamine. Use explosion-proof electrical equipment and fittings wherever methylamine is manufactured, handled, used, or stored (Harbison, 1998; Lewis, 1996; Sittig, 1991).
HANDLING
- Sources of ignition are prohibited wherever methylamine is handled, used, or stored. Use only non-sparking tools and equipment, especially when opening and closing containers of methylamine. Use explosion-proof electrical equipment and fittings wherever methylamine is manufactured, handled, used, or stored (Sittig, 1991).
STORAGE
Store methylamine in tightly closed containers; protect the containers from physical damage. Storage tanks should be made of steel and include proper dual pressure relief valves, a vapor absorption system, liquid level and pressure gauges, liquid and vapor transfer valves, and an adequate electrical ground. Ground and bond metal containers used to transfer 5 gallons or more of methylamine. Pipes, fittings, pumps, gauges, and other equipment should be made of steel, iron, or other material not subject to corrosion by methylamine. Methylamine is usually shipped in glass bottles, cans, drums, and tank cars (CGA, 1990; ITI, 1995; NFPA, 1994; Sittig, 1991).
- ROOM/CABINET RECOMMENDATIONS
Outdoor or detached storage is preferred for liquid methylamine. If liquid methylamine must be stored indoors, store in a standard combustible liquid storage room. Methylamine in gas form can be stored indoors if kept away from all sources of ignition or heat and kept in a cool, well-ventilated, and dry location (ITI, 1995; NFPA, 1994; Sittig, 1991).
References: (Pohanish & Greene, 1997; NFPA, 1994; Sittig, 1991) Mehtylamine may attack metals (aluminum, copper, tin, zinc, lead) and their alloys as well as rubber, some plastics and coatings (Pohanish & Greene, 1997).
-PERSONAL PROTECTION
SUMMARY
- RECOMMENDED PROTECTIVE CLOTHING - EMERGENCY RESPONSE GUIDEBOOK, GUIDE 118 (ERG, 2004)
Wear positive pressure self-contained breathing apparatus (SCBA). Wear chemical protective clothing that is specifically recommended by the manufacturer. It may provide little or no thermal protection. Structural firefighters' protective clothing provides limited protection in fire situations ONLY; it is not effective in spill situations where direct contact with the substance is possible.
- RECOMMENDED PROTECTIVE CLOTHING - EMERGENCY RESPONSE GUIDEBOOK, GUIDE 132 (ERG, 2004)
Wear positive pressure self-contained breathing apparatus (SCBA). Wear chemical protective that is specifically recommended by the manufacturer. It may provide little or no thermal protection. Structural firefighters' protective clothing provides limited protection in fire situations ONLY; it is not effective in spill situations where direct contact with the substance is possible.
- Methylamine is moderately toxic by inhalation and a severe skin and eye irritant. Avoid breathing vapors; keep upwind. Wear appropriate chemical protective clothing to prevent any possibility of skin contact. Do not handle broken or leaking containers unless wearing appropriate personal protective equipment. Avoid bodily contact with methylamine; wash away any methylamine which may have contacted the body with copious amounts of water or soap and water. Remove any clothing which becomes wet or contaminated with methylamine to avoid flammability hazard. Wear a positive pressure self-contained breathing apparatus to fight fires (AAR, 1998; (Lewis, 1996; NFPA, 1994; Sittig, 1991).
EYE/FACE PROTECTION
- Wear eye protection to prevent any possibility of eye contact (Sittig, 1991).
RESPIRATORY PROTECTION
- Refer to "Recommendations for respirator selection" in the NIOSH Pocket Guide to Chemical Hazards on TOMES Plus(R) for respirator information.
PROTECTIVE CLOTHING
- CHEMICAL PROTECTIVE CLOTHING. Search results for CAS 74-89-5.
-PHYSICAL HAZARDS
FIRE HAZARD
Editor's Note: Information from more than one emergency response guide is associated with this material. POTENTIAL FIRE OR EXPLOSION HAZARDS - EMERGENCY RESPONSE GUIDEBOOK, GUIDE 118 (ERG, 2004) EXTREMELY FLAMMABLE. May be ignited by heat, sparks or flames. May form explosive mixtures with air. Vapors from liquefied gas are initially heavier than air and spread along ground. Vapors may travel to source of ignition and flash back. Some of these materials may react violently with water. Cylinders exposed to fire may vent and release flammable gas through pressure relief devices. Containers may explode when heated. Ruptured cylinders may rocket.
POTENTIAL FIRE OR EXPLOSION HAZARDS - EMERGENCY RESPONSE GUIDEBOOK, GUIDE 132 (ERG, 2004) Flammable/combustible materials. May be ignited by heat, sparks or flames. Vapors may form explosive mixtures with air. Vapors may travel to source of ignition and flash back. Most vapors are heavier than air. They will spread along ground and collect in low or confined areas (sewers, basements, tanks). Vapor explosion hazard indoors, outdoors or in sewers. Those substances designated with a "P" may polymerize explosively when heated or involved in a fire. Runoff to sewer may create fire or explosion hazard. Containers may explode when heated. Many liquids are lighter than water.
If possible, stop any flow of gas before extinguishing a methylamine, anhydrous fire. When flow has been stopped, use flooding quanities of water as fog to extinguish the fire. Containers involved in the fire should also be cooled with flooding quantities of water. When attempting to control or extinguish the fire, move as far from the fire as possible (AAR, 1998; (NFPA, 1994; Sittig, 1991). If possible, stop any flow of liquid before extinguishing a liquid methylamine fire. Solid streams of water may be ineffective, however, water can be use in flooding quantities as fog, to knock down vapors and to cool any containers that may have been involved in the fire. It is important to thoroughly dilute liquid methylamine when it's on fire because it will continue to burn if concentrated. Extinguishing attempts should be made from as far from the fire as possible using an "alcohol" foam, dry chemical, or carbon dioxide extinguisher (AAR, 1998; (NFPA, 1994; Sittig, 1991).
- FLAMMABILITY CLASSIFICATION
- NFPA Flammability Rating for CAS74-89-5 (NFPA, 2002):
Listed as: Methylamine Flammability Rating: 4 (4) Extremely flammable. Materials which will rapidly vaporize at normal pressure and temperature and will burn readily. Including: gases, cryogenic materials, any liquid or gaseous material having a flash point below 73 degrees F and a boiling point below 100 degrees F, and materials which can form explosive mixtures with air.
- INITIATING OR CONTRIBUTING PROPERTIES
Methylamine is a flammable gas at ordinary temperature and pressure; it is a very dangerous fire and explosion hazard when exposed to heat, flame, or sparks and is easily ignited under most ambient conditions. Aqueous solutions of methylamine are flammable unless extensively diluted (AAR, 1998; (Lewis, 1996; Lewis, 1997; NFPA, 1994).
- FIRE CONTROL/EXTINGUISHING AGENTS
- FIRE PRECAUTIONS - EMERGENCY RESPONSE GUIDEBOOK, GUIDE 118 (ERG, 2004)
- FIRE PRECAUTIONS - EMERGENCY RESPONSE GUIDEBOOK, GUIDE 132 (ERG, 2004)
- SMALL FIRE PRECAUTIONS - EMERGENCY RESPONSE GUIDEBOOK, GUIDE 118 (ERG, 2004)
- SMALL FIRE PRECAUTIONS - EMERGENCY RESPONSE GUIDEBOOK, GUIDE 132 (ERG, 2004)
- LARGE FIRE PRECAUTIONS - EMERGENCY RESPONSE GUIDEBOOK, GUIDE 118 (ERG, 2004)
Water spray, fog or regular foam. Move containers from fire area if you can do it without risk. Damaged cylinders should be handled only by specialists.
- LARGE FIRE PRECAUTIONS - EMERGENCY RESPONSE GUIDEBOOK, GUIDE 132 (ERG, 2004)
Water spray, fog or alcohol-resistant foam. Move containers from fire area if you can do it without risk. Dike fire control water for later disposal; do not scatter the material. Do not get water inside containers.
- TANK OR CAR/TRAILER LOAD FIRE PRECAUTIONS - EMERGENCY RESPONSE GUIDEBOOK, GUIDE 132 (ERG, 2004)
Fight fire from maximum distance or use unmanned hose holders or monitor nozzles. Cool containers with flooding quantities of water until well after fire is out. Withdraw immediately in case of rising sound from venting safety devices or discoloration of tank. ALWAYS stay away from tanks engulfed in fire. For massive fire, use unmanned hose holders or monitor nozzles; if this is impossible, withdraw from area and let fire burn.
- TANK FIRE PRECAUTIONS - EMERGENCY RESPONSE GUIDEBOOK, GUIDE 118 (ERG, 2004)
Fight fire from maximum distance or use unmanned hose holders or monitor nozzles. Cool containers with flooding quantities of water until well after fire is out. Do not direct water at source of leak or safety devices; icing may occur. Withdraw immediately in case of rising sound from venting safety devices or discoloration of tank. ALWAYS stay away from tanks engulfed in fire.
- NFPA Extinguishing Methods for CAS74-89-5 (NFPA, 2002):
- NOTE: For fires involving methylamine, anhydrous, the best procedure is to stop the flow of gas before attempting to extinguish the fire. It is extremely dangerous to try to extinguish a fire while the gas is still flowing: an explosive gas/air cloud may form that, if ignited, may cause more damage than the original fire. It may be desirable to extinguish the flame with carbon dioxide or dry chemical to gain immediate access to valves to shut off the gas flow, but this must be done carefully. In many cases, it will be preferable to allow the fire to burn and protect exposures with water spray until the gas flow can be stopped (NFPA, 1994).
When heated to decomposition, methylamine emits toxic oxides of nitrogen and toxic amine vapors as well as carbon monoxide, carbon dioxide, and hydrocarbons (AAR, 1998; (ILO, 1998; Lewis, 1996; NFPA, 1994).
EXPLOSION HAZARD
- Methylamine is a flammable gas at ordinary temperature and pressure; it is a very dangerous explosion hazard when exposed to heat, flame, or sparks, and forms an explosive gas mixture with air. Under prolonged exposure to fire or intense heat, containers of methylamine, anhydrous may rupture violently and rocket (AAR, 1998; (Lewis, 1996; NFPA, 1994; Pohanish & Greene, 1997).
DUST/VAPOR HAZARD
- Methylamine vapors are heavier than air and may collect in low-lying areas or travel along the ground and cause a distant fire or explosion. Use water spray to cool and disperse vapors (AAR, 1998; (CGA, 1990; ILO, 1998; NFPA, 1994; Sittig, 1991).
- The vapors are toxic and corrosive; they are moderately toxic by inhalation and are a severe skin and eye irritant (CGA, 1990; ILO, 1998; Lewis, 1996; NFPA, 1994).
REACTIVITY HAZARD
- Methylamine can form an explosive gas mixture when exposed to air (Pohanish & Greene, 1997).
- It is incompatible with acids, organic anhydrides, isocyanates, halogenated compounds, acrylates, substituted allyls, alkylene oxides, ketones, aldehydes, alcohols, glycols, phenols, cresols, and strong oxidizers (such as chlorine) (Pohanish & Greene, 1997; ILO, 1998; NFPA, 1994; Sittig, 1991; Urben, 1996).
Methylamine is incompatible with epichlorohydrin, caprolactam solution, hypochlorite, and vinyl acetate (Pohanish & Greene, 1997; NFPA, 1994).
- It attacks metals and their alloys, and some plastics, rubber, and coatings (Pohanish & Greene, 1997).
Aluminum, copper, copper alloys (including brass and bronze), lead, tin, and zinc (including zinc alloys and galvanized surfaces), are corroded by methylamine (CGA, 1990; Pohanish & Greene, 1997).
- Mercury and methylamine react violently on contact resulting in fire and explosion. Instruments containing mercury must never be used with methylamine (CGA, 1990; ILO, 1998; NFPA, 1994).
- Methylamine also forms an explosive mixture with nitromethane (Lewis, 1996).
EVACUATION PROCEDURES
- Editor's Note: This material is not listed in the Table of Initial Isolation and Protective Action Distances.
- LARGE SPILL - PUBLIC SAFETY EVACUATION DISTANCES - EMERGENCY RESPONSE GUIDEBOOK, GUIDE 118 (ERG, 2004)
- LARGE SPILL - PUBLIC SAFETY EVACUATION DISTANCES - EMERGENCY RESPONSE GUIDEBOOK, GUIDE 132 (ERG, 2004)
Increase, in the downwind direction, as necessary, the isolation distance of at least at least 50 meters (150 feet) in all directions.
- FIRE - PUBLIC SAFETY EVACUATION DISTANCES - EMERGENCY RESPONSE GUIDEBOOK, GUIDE 118 (ERG, 2004)
If tank, rail car or tank truck is involved in a fire, ISOLATE for 1600 meters (1 mile) in all directions; also, consider initial evacuation for 1600 meters (1 mile) in all directions.
- FIRE - PUBLIC SAFETY EVACUATION DISTANCES - EMERGENCY RESPONSE GUIDEBOOK, GUIDE 132 (ERG, 2004)
If tank, rail car or tank truck is involved in a fire, ISOLATE for 800 meters (1/2 mile) in all directions; also, consider initial evacuation for 800 meters (1/2 mile) in all directions.
- PUBLIC SAFETY MEASURES - EMERGENCY RESPONSE GUIDEBOOK, GUIDE 118 (ERG, 2004)
CALL Emergency Response Telephone Number on Shipping Paper first. If Shipping Paper not available or no answer, refer to appropriate telephone number: MEXICO: SETIQ: 01-800-00-214-00 in the Mexican Republic; For calls originating in Mexico City and the Metropolitan Area: 5559-1588; For calls originating elsewhere, call: 011-52-555-559-1588.
CENACOM: 01-800-00-413-00 in the Mexican Republic; For calls originating in Mexico City and the Metropolitan Area: 5550-1496, 5550-1552, 5550-1485, or 5550-4885; For calls originating elsewhere, call: 011-52-555-550-1496, or 011-52-555-550-1552; 011-52-555-550-1485, or 011-52-555-550-4885.
ARGENTINA: CIQUIME: 0-800-222-2933 in the Republic of Argentina; For calls originating elsewhere, call: +54-11-4613-1100.
BRAZIL: PRÓ-QUÍMICA: 0-800-118270 (Toll-free in Brazil); For calls originating elsewhere, call: +55-11-232-1144 (Collect calls are accepted).
COLUMBIA: CISPROQUIM: 01-800-091-6012 in Colombia; For calls originating in Bogotá, Colombia, call: 288-6012; For calls originating elsewhere, call: 011-57-1-288-6012.
CANADA: UNITED STATES:
For additional details see the section entitled "WHO TO CALL FOR ASSISTANCE" under the ERG Instructions. As an immediate precautionary measure, isolate spill or leak area for at least 100 meters (330 feet) in all directions. Keep unauthorized personnel away. Stay upwind. Many gases are heavier than air and will spread along ground and collect in low or confined areas (sewers, basements, tanks). Keep out of low areas. Ventilate closed spaces before entering.
- PUBLIC SAFETY MEASURES - EMERGENCY RESPONSE GUIDEBOOK, GUIDE 132(ERG, 2004)
CALL Emergency Response Telephone Number on Shipping Paper first. If Shipping Paper not available or no answer, refer to appropriate telephone number: MEXICO: SETIQ: 01-800-00-214-00 in the Mexican Republic; For calls originating in Mexico City and the Metropolitan Area: 5559-1588; For calls originating elsewhere, call: 011-52-555-559-1588.
CENACOM: 01-800-00-413-00 in the Mexican Republic; For calls originating in Mexico City and the Metropolitan Area: 5550-1496, 5550-1552, 5550-1485, or 5550-4885; For calls originating elsewhere, call: 011-52-555-550-1496, or 011-52-555-550-1552; 011-52-555-550-1485, or 011-52-555-550-4885.
ARGENTINA: CIQUIME: 0-800-222-2933 in the Republic of Argentina; For calls originating elsewhere, call: +54-11-4613-1100.
BRAZIL: PRÓ-QUÍMICA: 0-800-118270 (Toll-free in Brazil); For calls originating elsewhere, call: +55-11-232-1144 (Collect calls are accepted).
COLUMBIA: CISPROQUIM: 01-800-091-6012 in Colombia; For calls originating in Bogotá, Colombia, call: 288-6012; For calls originating elsewhere, call: 011-57-1-288-6012.
CANADA: UNITED STATES:
For additional details see the section entitled "WHO TO CALL FOR ASSISTANCE" under the ERG Instructions. As an immediate precautionary measure, isolate spill or leak area for at least 50 meters (150 feet) in all directions. Keep unauthorized personnel away. Stay upwind. Keep out of low areas. Ventilate closed spaces before entering.
- AIHA ERPG Values for CAS74-89-5 (AIHA, 2006):
Listed as Monomethylamine ERPG-1 (units = ppm): 10 ERPG-2 (units = ppm): 100 ERPG-3 (units = ppm): 500 Under Ballot, Review, or Consideration: No Definitions: ERPG-1: The ERPG-1 is the maximum airborne concentration below which it is believed nearly all individuals could be exposed for up to one hour without experiencing more than mild, transient adverse health effects or perceiving a clearly defined objectionable odor. ERPG-2: The ERPG-2 is the maximum airborne concentration below which it is believed nearly all individuals could be exposed for up to one hour without experiencing or developing irreversible or other serious health effects or symptoms that could impair an individual's ability to take protective action. ERPG-3: The ERPG-3 is the maximum airborne concentration below which it is believed nearly all individuals could be exposed for up to one hour without experiencing or developing life-threatening health effects.
- DOE TEEL Values for CAS74-89-5 (U.S. Department of Energy, Office of Emergency Management, 2010):
- AEGL Values for CAS74-89-5 (National Research Council, 2010; National Research Council, 2009; National Research Council, 2008; National Research Council, 2007; NRC, 2001; NRC, 2002; NRC, 2003; NRC, 2004; NRC, 2004; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2006; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2007; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2005; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2005; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2007; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2006; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2006; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2006; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2006; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2006; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2006; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2006; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2006; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2006; United States Environmental Protection Agency Office of Pollution Prevention and Toxics, 2006; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2006; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2007; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2007; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2007; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2007; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2007; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2009; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2009; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2009; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2009; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2009; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2009; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2009; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2009; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2009; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2009; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2009; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2009; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2009; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2007; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2006; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2006; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2006; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2007; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2007; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2007; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2007; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2007; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2005; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2005; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2005; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2005; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2005; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2005; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2005; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2005; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2007; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2005; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2006; 62 FR 58840, 1997; 65 FR 14186, 2000; 65 FR 39264, 2000; 65 FR 77866, 2000; 66 FR 21940, 2001; 67 FR 7164, 2002; 68 FR 42710, 2003; 69 FR 54144, 2004):
Listed as: Monomethylamine Proposed Value: AEGL-1 10 min exposure: ppm: 15 ppm mg/m3: 19 mg/m(3)
30 min exposure: ppm: 15 ppm mg/m3: 19 mg/m(3)
1 hr exposure: ppm: 15 ppm mg/m3: 19 mg/m(3)
4 hr exposure: ppm: 15 ppm mg/m3: 19 mg/m(3)
8 hr exposure: ppm: 15 ppm mg/m3: 19 mg/m(3)
Definitions: AEGL-1 is the airborne concentration of a substance above which it is predicted that the general population, including susceptible individuals, could experience notable discomfort, irritation, or certain asymptomatic non-sensory effects. However, the effects are not disabling, are transient, and are reversible upon cessation of exposure.
Listed as: Monomethylamine Proposed Value: AEGL-2 10 min exposure: ppm: 160 ppm mg/m3: 200 mg/m(3)
30 min exposure: ppm: 92 ppm mg/m3: 120 mg/m(3)
1 hr exposure: ppm: 64 ppm mg/m3: 80 mg/m(3)
4 hr exposure: ppm: 31 ppm mg/m3: 39 mg/m(3)
8 hr exposure: ppm: 21 ppm mg/m3: 27 mg/m(3)
Definitions: AEGL-2 is the airborne concentration of a substance above which it is predicted that the general population, including susceptible individuals, could experience irreversible or other serious, long-lasting adverse health effects or an impaired ability to escape.
Listed as: Monomethylamine Proposed Value: AEGL-3 10 min exposure: ppm: 910 ppm mg/m3: 1200 mg/m(3)
30 min exposure: ppm: 510 ppm mg/m3: 650 mg/m(3)
1 hr exposure: ppm: 350 ppm mg/m3: 440 mg/m(3)
4 hr exposure: ppm: 170 ppm mg/m3: 220 mg/m(3)
8 hr exposure: ppm: 110 ppm mg/m3: 140 mg/m(3)
Definitions: AEGL-3 is the airborne concentration of a substance above which it is predicted that the general population, including susceptible individuals, could experience life-threatening health effects or death.
- NIOSH IDLH Values for CAS74-89-5 (National Institute for Occupational Safety and Health, 2007):
IDLH: 100 ppm Note(s): Not Listed
CONTAINMENT/WASTE TREATMENT OPTIONS
SPILL OR LEAK PRECAUTIONS - EMERGENCY RESPONSE GUIDEBOOK, GUIDE 118 (ERG, 2004) ELIMINATE all ignition sources (no smoking, flares, sparks or flames in immediate area). All equipment used when handling the product must be grounded. Fully encapsulating, vapor protective clothing should be worn for spills and leaks with no fire. Do not touch or walk through spilled material. Stop leak if you can do it without risk. If possible, turn leaking containers so that gas escapes rather than liquid. Use water spray to reduce vapors or divert vapor cloud drift. Avoid allowing water runoff to contact spilled material. Do not direct water at spill or source of leak. Isolate area until gas has dispersed.
SPILL OR LEAK PRECAUTIONS - EMERGENCY RESPONSE GUIDEBOOK, GUIDE 132 (ERG, 2004) Fully encapsulating, vapor protective clothing should be worn for spills and leaks with no fire. ELIMINATE all ignition sources (no smoking, flares, sparks or flames in immediate area). All equipment used when handling the product must be grounded. Do not touch or walk through spilled material. Stop leak if you can do it without risk. Prevent entry into waterways, sewers, basements or confined areas. A vapor suppressing foam may be used to reduce vapors. Absorb with earth, sand or other non-combustible material and transfer to containers (except for Hydrazine). Use clean non-sparking tools to collect absorbed material.
RECOMMENDED PROTECTIVE CLOTHING - EMERGENCY RESPONSE GUIDEBOOK, GUIDE 118 (ERG, 2004) Wear positive pressure self-contained breathing apparatus (SCBA). Wear chemical protective clothing that is specifically recommended by the manufacturer. It may provide little or no thermal protection. Structural firefighters' protective clothing provides limited protection in fire situations ONLY; it is not effective in spill situations where direct contact with the substance is possible.
RECOMMENDED PROTECTIVE CLOTHING - EMERGENCY RESPONSE GUIDEBOOK, GUIDE 132 (ERG, 2004) Wear positive pressure self-contained breathing apparatus (SCBA). Wear chemical protective that is specifically recommended by the manufacturer. It may provide little or no thermal protection. Structural firefighters' protective clothing provides limited protection in fire situations ONLY; it is not effective in spill situations where direct contact with the substance is possible.
In the case of a methylamine (anhydrous or aqueous solution) leak, keep all sources of ignition (eg, sparks, flames, smoking) away from the leak area and attempt to stop the leak, if it can be done safely. Approach the leak from upwind. Water spray should be used to knock down vapors, protect personnel and dilute the spill so that it is less flammable. To neutralize diluted pools, use 5% sulfuric acid. Water run-off must be kept out of water sources and sewers and controlled for proper disposal (AAR, 1998; (NFPA, 1994). If a methylamine (anhydrous or aqueous solution) leak occurs on land attempt to control the leak by digging a pit, pond, lagoon or other holding area for containment. Also, dike leak or run-off with soil, sand bags, foamed polyurethane or foamed concrete. Use fly ash, cement powder, or commercial sorbents to absorb bulk liquid and to neutralize the bulk liquid, use sodium bisulfate (NaHSO4). For methylamine, aqueous solutions, a "universal" gelling agents can be used to immobilize the spill (AAR, 1998). When a methylamine (anhydrous or aqueous solution) leak occurs in water, control the spill using natural barriers or oil control booms. To aid the effectiveness of the booms, solidify the encircled spill using a "universal" gelling agent. An EPA approved surface active agent (eg, detergent, soaps, alcohols) should also be used. For spills in concentrations of 10 ppm or greater, use ten times the spilled amount of activated carbon and neutralize with sodium bisulfate (NaHSO4). Remove immobilized masses of pollutants and precipitates using mechanical dreges or lifts (AAR, 1998). If a methylamine (anhydrous or aqueous solution) leak occurs in the air, use water spray to knock down vapors. Dike the run-off for containment and neutralize with sodium bisulfate (NaHSO4).
Methylamine system leaks can be detected using moistened, red litmus paper, which will turn blue if methylamine is present in air. Also, an open bottle of muriatic acid will fume if methylamine is in the air. NEVER use flames to test for leaks. If a small leak is discovered, a wet rag placed on the site of the leak will prevent further contamination until repairs can be made (CGA, 1990). Access to spill or leak area should be restricted to only those employees who are wearing appropriate chemical protective clothing and involved in clean-up effort. Sources of ignition should be removed from the area and the area ventilated. If the leak cannot be stopped in place and it is coming from a cylinder that can be moved, move the cylinder to a safe place in the open air, and repair the leak. If the leak cannot be repaired or stopped, allow the cylinder to empty. Use sodium bisulfate (NaHSO4) to neutralize the leak and add water (ITI, 1995; Sittig, 1991).
To dispose of methylamine, anhydrous, slowly discharge gas into a scrubber or another suitable container that contains a 10-20% aqueous acid solution (ie, sulfuric, hydrochloric, etc.). The scrubber or container should be equipped with a check valve or reverse flow trap in the line. This will prevent the acid solution from drawing back into the cylinders and reacting with methylamine. The resulting solution should be disposed of according to local, state, and federal regulations (CGA, 1990). Waste management activities associated with material disposition are unique to individual situations. Proper waste characterization and decisions regarding waste management should be coordinated with the appropriate local, state, or federal authorities to ensure compliance with all applicable rules and regulations.
To dispose of methylamine, use controlled incineration in a incinerator equipped with a scrubber or thermal unit, to reduce nitrogen emissions (ITI, 1995; Sittig, 1991).
-ENVIRONMENTAL HAZARD MANAGEMENT
POLLUTION HAZARD
Environmental release of methylamine may occur through various waste streams associated with its manufacture and use as chemical intermediate for industrial production of dyes, pharmaceuticals, photographic developers, insecticides, and fungicides. It is also used as a fuel additive and rocket propellant and may be introduced to the environment through those uses (HSDB, 2005; Howard, 1990). Methylamine can occur naturally in herring brine, dog urine, many vegetables and foods, and certain wild plants (e.g., Mentha aquatica) (HSDB, 2005; Howard, 1990).
ENVIRONMENTAL FATE AND KINETICS
Methylamine typically exists solely as a gas in the ambient atmosphere, given a vapor pressure of 2650 mm Hg at 25 degrees C (HSDB, 2005). Methylamine degrades rapidly in the atmosphere through reaction with photochemically-produced hydroxyl radicals. The half-life for this reaction is about 18 hours (range of 3 to 22 hours), based on a rate constant of 2.2 x 10(-11) cm(3)/molec-sec (26 degrees C) and a hydroxyl radical concentrations of 5 x 10(5) molecules/cm(3) and 4.1 x 10(5) molecules/cm(3) (HSDB, 2005; Verschueren, 2001; Howard, 1990). Dissolution of methylamine into raindrops is perhaps the most important physical atmospheric removal process (Howard, 1990). The reaction of methylamine and ozone, or methylamine and oxygen atoms are not important environmental fate processes. The half-life for these two reactions are about 1 and 1.6 years, respectively (Howard, 1990). Release tests demonstrate atmospheric plume velocities for methylamine range from 0.2087 to 0.4000 m/sec. Test conditions entailed plume release through a 6.35 mm orifice, tank pressures of 99.63-26,854 kPa, a 270-kg storage cylinder pressurized to 150-250 kPa, and tank storage temperatures of -3.72 to 16.32 degrees K (Lantzy et al, 1990). Other tests demonstrate that superheats (19 K or higher) can completely atomize methylamine plumes into a dense mist (flash atomization) with no measurable methylamine raining out. Superheats at less than 9 K can create plumes of large droplets (hydraulic atomization) which can rain out virtually all the methylamine (Lantzy et al, 1990).
SURFACE WATER Methylamine typically volatilizes from water surfaces, given a Henry's Law constant of 1.11 x 10(-5) atm-m(3)/mole (HSDB, 2005). Estimated volatilization half-lives for methylamine are 1.9 days from a model river (1 m deep, 1 m/sec flow rate, 3 m/sec wind speed) and 16 days from a model lake (1 m deep, 0.05 m/sec flow rate, 0.5 m/sec wind speed) (HSDB, 2005).
Hydrolysis is not an important removal process for methylamine in aqueous environments. The estimated hydrolytic half-life of methylamine is 199 years, based on a hydroxyl radical rate constant of 1.1 x 10(7)/M-sec at pH 5 and a hydroxyl radical concentration of 10(-7) M (Verschueren, 2001; Howard, 1990). Methylamine's potential to sorb to organic matter in sediment or suspended solids is weak, given its estimated organic carbon partition coefficient (Koc) of 12 (Howard, 1990). Biodegradation is considered an important environmental fate process for methylamine in aqueous systems (HSDB, 2005; Howard, 1990).
GROUND WATER
TERRESTRIAL Aqueous methylamine solutions can rapidly volatilize from surface soil. Methylamine can potentially volatilize from dry surface soil given its vapor pressure of 2650 mm Hg (HSDB, 2005; Howard, 1990). Methylamine is expected to be moderately mobile in most soils, given organic carbon partition coefficients (Koc) of 389 and 449, observed on Alfisol agricultural soil (1.25% organic C) and Lake Constance subliminic sediment (1.58% organic C), respectively (HSDB, 2005).
ABIOTIC DEGRADATION
- If released to the environment, methylamine usually exists solely in its vapor phase, where it rapidly degrades through reaction with photochemically-produced hydroxyl radicals (half-life of 3 to 22 hours). Dissolution of methylamine into raindrops is an important physical atmospheric removal process. Methylamine can volatilize from surface waters, but this is not an important environmental fate process. Aqueous solutions of methylamine will volatilize from surface soil. Methylamine does not adsorb strongly to organic matter and can leach through soil to groundwater. Methylamine generally biodegrades in water and soil environments (HSDB, 2005; Howard, 1990).
BIODEGRADATION
- Biodegradation screening tests show several bacteria species can successfully degrade methylamine under aerobic and anaerobic conditions (HSDB, 2005; Howard, 1990).
The aerobic bacterium, Pseudomonas sp MA, can grow using methylamine as a sole carbon, nitrogen, and energy source. Other non-methylotrophic bacteria can grow using methylamine as the sole nitrogen source in the presence of an organic compound mixture, but not with methylamine as the sole carbon source (HSDB, 2005; Howard, 1990). Mixed cultures from anaerobic marine sediments and pure cultures of Methanosarcina barkeri can degrade methylamine under aerobic conditions (HSDB, 2005; Howard, 1990).
BIOACCUMULATION
Methylamine's bioconcentration potential in fish and other aquatic organisms is generally considered low, given an estimated bioconcentration factor (BCF) less than 1 (HSDB, 2005; Howard, 1990).
AQUATIC Reported bioaccumulation ratios for the giant kelp, Macrocystis pyrifera, range from 141 to 183, given an aqueous methylamine concentration of 2.15-8.14mcM (Howard, 1990).
Methylamine's bioconcentration potential is generally considered low. Its estimated bioconcentration factor (BCF) is less than 1, based on a log octanol water partition coefficient (log Kow) of -0.57 (HSDB, 2005; Howard, 1990).
ENVIRONMENTAL TOXICITY
EC0 - WATER FLEA (Daphnia): 480 mg/L (Verschueren, 2001) EC50 - BACTERIA (Photobacterium phosphoreum): 35 mg/L for 5 min (Microtox test) (Verschueren, 2001) LC0 - ALGAE (Scenedesmus): 4 mg/L (Verschueren, 2001) LC0 - BACTERIA (E. coli): 1,000 mg/L(Verschueren, 2001) LC50 - FISH (Creek chub): 10-30 mg/L for 24H (Verschueren, 2001)
-PHYSICAL/CHEMICAL PROPERTIES
MOLECULAR WEIGHT
DESCRIPTION/PHYSICAL STATE
- In its anhydrous form, methylamine is a flammable, colorless, toxic gas at normal temperature and pressure. It is easily liquefied and becomes a fuming liquid when cooled in an ice and salt mixture. Aqueous solutions of methylamine are a solution of the gas in water. Methylamine has a distinct and disagreeable fishy odor below 100 ppm (AAR, 1998; (ACGIH, 1991; Ashford, 1994; Budavari, 1996; CGA, 1990; Clayton & Clayton, 1994; Harbison, 1998; Lewis, 1997; Lewis, 1996; Verschueren, 1983).
Methylamine's distint odor can be detected at 10 ppm. The odor is strong at 20-100 ppm, and is intolerably ammonical at 100-500 ppm (CGA, 1990; Clayton & Clayton, 1994).
PH
- Methylamine is a medium strong base and is a slightly stronger base than ammonia (CGA, 1990; ILO, 1998).
pKb = 3.35 (at 25 degrees C) (ACGIH, 1991; Clayton & Clayton, 1994; Budavari, 1996; Snyder et al, 1990) pKa = 10.65 (Clayton & Clayton, 1994) pKa = 10.657 (Howard, 1990)
VAPOR PRESSURE
- 2160 mmHg (at 20 degrees C) (Snyder et al, 1990)
- 2622 mmHg (at 25 degrees C) (NFPA, 1994)
- 2650 mmHg (at 25 degrees C) (Howard, 1990)
- 43.5 psia; 300 kPa abs (at 20 degrees C; 68 degrees F) (CGA, 1990)
- 3.1 atm (at 20 degrees C) (Verschueren, 1983)
- 2 atm (at 25 degrees C) (Clayton & Clayton, 1983)
- 4.3 atm (at 30 degrees C) (Verschueren, 1983)
- NOTE: The vapor pressure of aqueous solutions of methylamine will range from 215-500 mmHg (NFPA, 1994).
SPECIFIC GRAVITY
- OTHER TEMPERATURE AND/OR PRESSURE
GAS: 0.662 (at 20/4 degrees C) (Lewis, 1996) LIQUID: 0.699 (at -10.8/4 degrees C) (Budavari, 1996; Lewis, 1996)
DENSITY
- OTHER TEMPERATURE AND/OR PRESSURE
LIQUID: 0.67 kg/L (at 4 degrees C) (Ashford, 1994) LIQUID: 663.2 kg/m(3); 41.4 lb/ft(3) (at 21.1 degrees C; 70 degrees F) (CGA, 1990) LIQUID: 642.3 kg/m(3); 40.1 lb/ft(3) (at 40.5 degrees C; 105 degrees F) (CGA, 1990) LIQUID: 637.5 kg/m(3); 39.8 lb/ft(3) (at 46.1 degrees C; 115 degrees F) (CGA, 1990) LIQUID: 627.9 kg/m(3); 39.2 lb/ft(3) (at 54.4 degrees C; 130 degrees F) (CGA, 1990)
FREEZING/MELTING POINT
-92.5 degrees C (Lewis, 1997) -93.5 degrees C; -136.3 degrees F (at 1 atm) (CGA, 1990) -94 degrees C (Ashford, 1994)
-92.5 degrees C (Verschueren, 1983) -93.5 degrees C (ACGIH, 1991; Budavari, 1996; Clayton & Clayton, 1994; Howard, 1990; Lewis, 1996; Snyder et al, 1990) -94 degrees C; -136 degrees F (ILO, 1998; NFPA, 1994)
BOILING POINT
- -6 degrees C; 21 degrees F (Ashford, 1994; NFPA, 1994)
- -6.3 degrees C (at 760 mmHg) (ACGIH, 1991; Budavari, 1996; Clayton & Clayton, 1994; Howard, 1990; ILO, 1998; Lewis, 1996; Snyder et al, 1990)
- -6.33 degrees C; 20.6 degrees F (at 1 atm) (CGA, 1990)
- -6.5 degrees C (Verschueren, 1983)
- -6.79 degrees C (Lewis, 1997)
- -19.7 degrees C (at 400 mmHg) (Budavari, 1996)
- -32.4 degrees C (at 200 mmHg) (Budavari, 1996)
- -43.7 degrees C (at 100 mmHg) (Budavari, 1996)
- -73.8 degrees C (at 10 mmHg) (Budavari, 1996)
- NOTE: Boiling temperatures for aqueous solutions will be about 18.3-29.4 degrees C (65-85 degrees F) higher than those listed above (NFPA, 1994).
FLASH POINT
- 32 degrees F (closed cup) (Lewis, 1996)
- 0 degrees C; 32.5 degrees F (Budavari, 1996)
- 1.1 degrees C; 34 degrees F (30% solution) (TOC) (Clayton & Clayton, 1994)
- -10 degrees C; 14 degrees F (gas) (Lewis, 1997)
AUTOIGNITION TEMPERATURE
- 430 degrees C; 806 degrees F (CGA, 1990; ILO, 1998; Lewis, 1996; Lewis, 1997; NFPA, 1994)
EXPLOSIVE LIMITS
4.9% (NFPA, 1994) 4.95% (Lewis, 1996)
20.7% (NFPA, 1994) 20.75% (Lewis, 1996)
SOLUBILITY
Methylamine is very soluble in water (ACGIH, 1991; Ashford, 1994; Clayton & Clayton, 1994; ILO, 1998; Lewis, 1997; NFPA, 1994). One volume of water dissolves 1154 volumes of methylamine gas at 12.5 degrees C and 959 volumes at 25 degrees C (Budavari, 1996). The solubility of methylamine in water, wt/wt, is 108% at 25 degrees C (77 degrees F) and 1 atm. This has also been expressed as 1,080,000 mg/L at 25 degrees C (CGA, 1990; Howard, 1990) Synder et al, 1990).
It is soluble in alcohol and oxygenated solvents and miscible with ether (ACGIH, 1991; Ashford, 1994; Lewis, 1996; Lewis, 1997) Synder et al, 1990).
OCTANOL/WATER PARTITION COEFFICIENT
HENRY'S CONSTANT
- 1.11x10(-5) atm-m(3)/mol (at 25 degrees C) (Howard, 1990)
OTHER/PHYSICAL
pKb = 3.35 (at 25 degrees C) (ACGIH, 1991; Clayton & Clayton, 1994; Snyder et al, 1990) pKa = 10.65 (Clayton & Clayton, 1994) pKa = 10.657 (Howard, 1990)
-REFERENCES
GENERAL BIBLIOGRAPHY- 40 CFR 372.28: Environmental Protection Agency - Toxic Chemical Release Reporting, Community Right-To-Know, Lower thresholds for chemicals of special concern. National Archives and Records Administration (NARA) and the Government Printing Office (GPO). Washington, DC. Final rules current as of Apr 3, 2006.
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- 62 FR 58840: Notice of the National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances - Proposed AEGL Values, Environmental Protection Agency, NAC/AEGL Committee. National Archives and Records Administration (NARA) and the Government Publishing Office (GPO), Washington, DC, 1997.
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- 65 FR 39264: Notice of the National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances - Proposed AEGL Values, Environmental Protection Agency, NAC/AEGL Committee. National Archives and Records Administration (NARA) and the Government Publishing Office (GPO), Washington, DC, 2000.
- 65 FR 77866: Notice of the National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances - Proposed AEGL Values, Environmental Protection Agency, NAC/AEGL Committee. National Archives and Records Administration (NARA) and the Government Publishing Office (GPO), Washington, DC, 2000.
- 66 FR 21940: Notice of the National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances - Proposed AEGL Values, Environmental Protection Agency, NAC/AEGL Committee. National Archives and Records Administration (NARA) and the Government Publishing Office (GPO), Washington, DC, 2001.
- 67 FR 7164: Notice of the National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances - Proposed AEGL Values, Environmental Protection Agency, NAC/AEGL Committee. National Archives and Records Administration (NARA) and the Government Publishing Office (GPO), Washington, DC, 2002.
- 68 FR 42710: Notice of the National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances - Proposed AEGL Values, Environmental Protection Agency, NAC/AEGL Committee. National Archives and Records Administration (NARA) and the Government Publishing Office (GPO), Washington, DC, 2003.
- 69 FR 54144: Notice of the National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances - Proposed AEGL Values, Environmental Protection Agency, NAC/AEGL Committee. National Archives and Records Administration (NARA) and the Government Publishing Office (GPO), Washington, DC, 2004.
- ACGIH: Documentation of the Threshold Limit Values and Biological Exposure Indices, Vol 1, 6th ed, Am Conference of Govt Ind Hyg, Inc, Cincinnati, OH, 1991.
- AIHA: 2006 Emergency Response Planning Guidelines and Workplace Environmental Exposure Level Guides Handbook, American Industrial Hygiene Association, Fairfax, VA, 2006.
- American Conference of Governmental Industrial Hygienists : ACGIH 2010 Threshold Limit Values (TLVs(R)) for Chemical Substances and Physical Agents and Biological Exposure Indices (BEIs(R)), American Conference of Governmental Industrial Hygienists, Cincinnati, OH, 2010.
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- Ashford R: Ashford's Dictionary of Industrial Chemicals, Wavelength Publications Ltd, London, England, 1994.
- Bata Shoe Company: Industrial Footwear Catalog, Bata Shoe Company, Belcamp, MD, 1995.
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