methylhydrazine

H350: May cause cancer [Danger Carcinogenicity]

P203, P280, P318, P405, and P501 (click each P-code to see the statement)

H225 (86.1%): Highly Flammable liquid and vapor [Danger Flammable liquids]

H300+H310+H330 (30.7%): Fatal if swallowed, in contact with skin or if inhaled [Danger Acute toxicity, oral; acute toxicity, dermal; acute toxicity, inhalation]

H300 (97.5%): Fatal if swallowed [Danger Acute toxicity, oral]

H310 (97.5%): Fatal in contact with skin [Danger Acute toxicity, dermal]

H314 (92.4%): Causes severe skin burns and eye damage [Danger Skin corrosion/irritation]

H317 (64.7%): May cause an allergic skin reaction [Warning Sensitization, Skin]

H318 (58.4%): Causes serious eye damage [Danger Serious eye damage/eye irritation]

H330 (98.3%): Fatal if inhaled [Danger Acute toxicity, inhalation]

H334 (20.6%): May cause allergy or asthma symptoms or breathing difficulties if inhaled [Danger Sensitization, respiratory]

H350 (98.7%): May cause cancer [Danger Carcinogenicity]

H400 (73.5%): Very toxic to aquatic life [Warning Hazardous to the aquatic environment, acute hazard]

H410 (76.9%): Very toxic to aquatic life with long lasting effects [Warning Hazardous to the aquatic environment, long-term hazard]

H411 (20.6%): Toxic to aquatic life with long lasting effects [Hazardous to the aquatic environment, long-term hazard]

P203, P210, P233, P240, P241, P242, P243, P260, P261, P262, P264, P264+P265, P270, P271, P272, P273, P280, P284, P301+P316, P301+P330+P331, P302+P352, P302+P361+P354, P303+P361+P353, P304+P340, P305+P354+P338, P316, P317, P318, P320, P321, P330, P333+P317, P342+P316, P361+P364, P362+P364, P363, P370+P378, P391, P403, P403+P233, P403+P235, P405, and P501 (click each P-code to see the statement)

Aggregated GHS information provided per 238 reports by companies from 13 notifications to the ECHA C&L Inventory. Each notification may be associated with multiple companies.

Information may vary between notifications depending on impurities, additives, and other factors. The percentage value in parenthesis indicates the notified classification ratio from companies that provide hazard codes. Only hazard codes with percentage values above 10% are shown. For more detailed information, please visit ECHA C&L website.

H400: Very toxic to aquatic life [Warning Hazardous to the aquatic environment, acute hazard]

H410: Very toxic to aquatic life with long lasting effects [Warning Hazardous to the aquatic environment, long-term hazard]

P273, P391, and P501 (click each P-code to see the statement)

H224: Extremely flammable liquid and vapor [Danger Flammable liquids]

H300: Fatal if swallowed [Danger Acute toxicity, oral]

H310: Fatal in contact with skin [Danger Acute toxicity, dermal]

H315: Causes skin irritation [Warning Skin corrosion/irritation]

H319: Causes serious eye irritation [Warning Serious eye damage/eye irritation]

H330: Fatal if inhaled [Danger Acute toxicity, inhalation]

H351: Suspected of causing cancer [Warning Carcinogenicity]

H361: Suspected of damaging fertility or the unborn child [Warning Reproductive toxicity]

H370: Causes damage to organs [Danger Specific target organ toxicity, single exposure]

H372: Causes damage to organs through prolonged or repeated exposure [Danger Specific target organ toxicity, repeated exposure]

P203, P210, P233, P240, P241, P242, P243, P260, P262, P264, P264+P265, P270, P271, P280, P284, P301+P316, P302+P352, P303+P361+P353, P304+P340, P305+P351+P338, P308+P316, P316, P318, P319, P320, P321, P330, P332+P317, P337+P317, P361+P364, P362+P364, P370+P378, P403+P233, P403+P235, P405, and P501 (click each P-code to see the statement)

P203, P260, P262, P264, P270, P271, P280, P284, P301+P316, P302+P352, P304+P340, P316, P318, P319, P320, P321, P330, P361+P364, P403+P233, P405, and P501 (click each P-code to see the statement)

Fresh air, rest. Artificial respiration may be needed. Refer for medical attention.

First rinse with plenty of water for at least 15 minutes, then remove contaminated clothes and rinse again. Refer for medical attention .

First rinse with plenty of water for several minutes (remove contact lenses if easily possible), then refer for medical attention.

Rinse mouth. Do NOT induce vomiting. Give one or two glasses of water to drink. Refer for medical attention .

Warning: Symptoms may be delayed from hours to days. Caution is advised.

Signs and Symptoms of Acute Methyl Hydrazine Exposure: Symptoms of acute exposure to methyl hydrazine may include facial numbness, facial swelling, and increased salivation. Headache, twitching, seizure, convulsions, and coma may also occur. Gastrointestinal signs and symptoms include anorexia, nausea, and vomiting. Pulmonary edema and hypotension (low blood pressure) are common. Methyl hydrazine is toxic to the liver, ruptures red blood cells, and may cause kidney damage. Contact with the skin, eyes, or mucous membranes may result in severe irritation and permanent damage.

Emergency Life-Support Procedures: Acute exposure to methyl hydrazine may require decontamination and life support for the victims. Emergency personnel should wear protective clothing appropriate to the type and degree of contamination. Air-purifying or supplied-air respiratory equipment should also be worn, as necessary. Rescue vehicles should carry supplies such as plastic sheeting and disposable plastic bags to assist in preventing spread of contamination.

Inhalation Exposure:

1. Move victims to fresh air. Emergency personnel should avoid self-exposure to methyl hydrazine.

2. Evaluate vital signs including pulse and respiratory rate, and note any trauma. If no pulse is detected, provide CPR. If not breathing, provide artificial respiration. If breathing is labored, administer oxygen or other respiratory support.

3. Obtain authorization and/or further instructions from the local hospital for administration of an antidote or performance of other invasive procedures.

4. RUSH to a health care facility.

Dermal/Eye Exposure:

1. Remove victims from exposure. Emergency personnel should avoid self- exposure to methyl hydrazine.

3. Remove contaminated clothing as soon as possible.

4. If eye exposure has occurred, eyes must be flushed with lukewarm water for at least 15 minutes.

5. Wash exposed skin areas THOROUGHLY with soap and water.

6. Obtain authorization and/or further instructions from the local hospital for administration of an antidote or performance of other invasive procedures.

7. RUSH to a health care facility.

Ingestion Exposure:

1. Evaluate vital signs including pulse and respiratory rate, and note any trauma. If no pulse is detected, provide CPR. If not breathing, provide artificial respiration. If breathing is labored, administer oxygen or other respiratory support.

2. Obtain authorization and/or further instructions from the local hospital for administration of an antidote or performance of other invasive procedures.

3. Give the victims water or milk: children up to 1 year old, 125 mL (4 oz or 1/2 cup); children 1 to 12 years old, 200 mL (6 oz or 3/4 cup); adults, 250 mL (8 oz or 1 cup). Water or milk should be given only if victims are conscious and alert.

4. Activated charcoal may be administered if victims are conscious and alert. Use 15 to 30 g (1/2 to 1 oz) for children, 50 to 100 g (1-3/4 to 3-1/2 oz) for adults, with 125 to 250 mL (1/2 to 1 cup) of water.

5. Promote excretion by administering a saline cathartic or sorbitol to conscious and alert victims. Children require 15 to 30 g (1/2 to 1 oz) of cathartic; 50 to 100 g (1-3/4 to 3-1/2 oz) is recommended for adults.

6. RUSH to a health care facility. (EPA, 1998)

General First Aid:

· Call 911 or emergency medical service.

· Ensure that medical personnel are aware of the material(s) involved, take precautions to protect themselves and avoid contamination.

· Move victim to fresh air if it can be done safely.

· Administer oxygen if breathing is difficult.

· If victim is not breathing:

-- DO NOT perform mouth-to-mouth resuscitation; the victim may have ingested or inhaled the substance.

-- If equipped and pulse detected, wash face and mouth, then give artificial respiration using a proper respiratory medical device (bag-valve mask, pocket mask equipped with a one-way valve or other device).

-- If no pulse detected or no respiratory medical device available, provide continuous compressions. Conduct a pulse check every two minutes or monitor for any signs of spontaneous respirations.

· Remove and isolate contaminated clothing and shoes.

· For minor skin contact, avoid spreading material on unaffected skin.

· In case of contact with substance, remove immediately by flushing skin or eyes with running water for at least 20 minutes.

· For severe burns, immediate medical attention is required.

· Effects of exposure (inhalation, ingestion, or skin contact) to substance may be delayed.

Wear positive pressure breathing apparatus and special (full) protective clothing. No skin surface should be exposed. Isolate area for 1/2-mile in all directions if a tank car or truck is involved in a fire.

For small fires, use dry chemical, carbon dioxide, water spray, and foam. For large fires, use water spray, fog, or foam. Keep unnecessary people away and isolate the hazardous area. Stay upwind and keep out of low-lying areas.

Fire exposed containers should be kept cool with water. Use water spray to disperse vapors and protect men attempting to stop a leak which has not ignited. Move container from fire area if it can be done without risk. (EPA, 1998)

Use water in large amounts, powder, alcohol-resistant foam, carbon dioxide. In case of fire: keep drums, etc., cool by spraying with water. Combat fire from a sheltered position.

Use flooding quantities of water. Use water spray to keep fire-exposed containers cool. Fight fire from protected location or maximum possible distance. Approach fire from upwind to avoid hazardous vapors and toxic decomposition products.

If material on fire or involved in fire: Do not extinguish fire unless flow can be stopped. Use water in flooding quantities as fog. Cool all affected containers with flooding quantities of water. Apply water from as far a distance as possible. Solid streams of water may be ineffective. Use "alcohol" foam, dry chemical or carbon dioxide.

Vapors are heavier than air and may travel to a source of ignition and flash back.

Prolonged exposure of the containers of the material to fire or heat may result in the spontaneous decomposition of the material & violent rupture of the container.

· CALL 911. Then call emergency response telephone number on shipping paper. If shipping paper not available or no answer, refer to appropriate telephone number listed on the inside back cover.

· Keep unauthorized personnel away.

· Stay upwind, uphill and/or upstream.

· Ventilate closed spaces before entering, but only if properly trained and equipped.

· ELIMINATE all ignition sources (no smoking, flares, sparks or flames) from 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.

Small Spill

· Absorb with earth, sand or other non-combustible material and transfer to containers for later disposal.

· Use clean, non-sparking tools to collect absorbed material.

Large Spill

· Dike far ahead of liquid spill for later disposal.

· Water spray may reduce vapor, but may not prevent ignition in closed spaces.

Excerpt from ERG Guide 131 [Flammable Liquids - Toxic]:

IMMEDIATE PRECAUTIONARY MEASURE: Isolate spill or leak area for at least 50 meters (150 feet) in all directions.

SPILL: See ERG Table 1 - Initial Isolation and Protective Action Distances on the UN/NA 1244 datasheet.

FIRE: If tank, rail tank car or highway tank 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. (ERG, 2024)

Immediate precautionary measure

· Isolate spill or leak area for at least 50 meters (150 feet) in all directions.

· For highlighted materials: see Table 1 - Initial Isolation and Protective Action Distances.

· For non-highlighted materials: increase the immediate precautionary measure distance, in the downwind direction, as necessary.

· If tank, rail tank car or highway tank 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.

Small spill:

- ISOLATE in all directions: 30 m (100 ft)

Large spill:

- ISOLATE in all directions: 150 m (500 ft)

- PROTECT people from downwind during DAY time: 0.3 km (0.2 mi)

- PROTECT people from downwind during NIGHT time: 0.6 km (0.4 mi)

- PROTECT people from downwind during DAY time: 1.5 km (0.9 mi)

- PROTECT people from downwind during NIGHT time: 2.2 km (1.4 mi)

Evacuate danger area! Consult an expert! Personal protection: complete protective clothing including self-contained breathing apparatus. Do NOT let this chemical enter the environment.

Wear butyl rubber gloves, self-contained breathing apparatus, eye protection and impervious clothing. Body shield should be available. Eliminate all sources of ignition and flammables. On skin or clothing. Wash skin immediately. Remove contaminated clothing at once. Spills: Cover spill with a 1:1:1 mixture by weight of sodium carbonate or calcium carbonate, clay cat litter (bentonite) and sand. Scoop the solid into a container, transport to the fume hood and slowly add to water allowing 20 ml water for each 1 g of methylhydrazine. Filter off the clay and sand. For each 1 g of methylhydrazine, place 41 ml (about 25% excess) of commercial laundry bleach (containing about 5.25% sodium hypochlorite) into a 3-necked round-bottom flask equipped with a stirrer, thermometer and dropping funnel. Add the aqueous methylhydrazine dropwise to the stirred hypochlorite solution, monitoring the rate of addition by rise in temperature. The temperature is maintained at 45-50 °C and addition takes about 1 hour. Stirring is continued for 2 hours until the temperature gradually falls to room temperature.

Generators of waste (equal to or greater than 100 kg/mo) containing this contaminant, EPA hazardous waste number P068, must conform with USEPA regulations in storage, transportation, treatment and disposal of waste.

Methyl hydrazine is a good candidate for liquid injection incineration with a temperature range of 650 to 1600 °C and a residence time of 0.1 to 2 seconds. Also a good candidate for rotary kiln incineration with a temperature range of 820 to 1,600 °C and residence times of seconds for liquids and gases; for solids hours. Also a good candidate fluidized bed incineration with a temperature range of 450 to 980 °C and residence times of seconds for liquids and gases; longer for solids.

Small Quantities. Wear butyl rubber gloves, laboratory coat and eye prolection. Work in the fume hood. Prepare a dilute (5%) aqueous solution of methylhydrazine by adding slowly to the appropriate volume of water. For each 1 g of methylhydrazine, place 41 ml (about 25% excess) of household laundry bleach (5.25% sodium hypochlorite) into a 3-necked round-bottom flask equipped with a stirrer, thermometer and dropping funnel. Add the aqueous methylhydrazine dropwise to the stirred hypochlorite solution, monitoring the rate of addition by rise in temperature. The temperature is maintained at 45-50 °C and addition takes about 1 hour. Stirring is continued for 2 hours until the temperature gradually falls to room temperature.

Incomplete reaction of hypochlorite with the methylated hydrazine fuels monomethylhydrazine and unsymmetrical dimethylhydrazine leads to a wide variety of byproducts, including N-nitrosoamines, which are believed to be highly carcinogenic.

SRP: The scientific literature for the use of contact lenses in industry is conflicting. The benefit or detrimental effects of wearing contact lenses depend not only upon the substance, but also on factors including the form of the substance, characteristics and duration of the exposure, the uses of other eye protection equipment, and the hygiene of the lenses. However, there may be individual substances whose irritating or corrosive properties are such that the wearing of contact lenses would be harmful to the eye. In those specific cases, contact lenses should not be worn. In any event, the usual eye protection equipment should be worn even when contact lenses are in place.

Excerpt from ERG Guide 131 [Flammable Liquids - Toxic]:

ELIMINATE all ignition sources (no smoking, flares, sparks or flames) from 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.

SMALL SPILL: Absorb with earth, sand or other non-combustible material and transfer to containers for later disposal. Use clean, non-sparking tools to collect absorbed material.

LARGE SPILL: Dike far ahead of liquid spill for later disposal. Water spray may reduce vapor, but may not prevent ignition in closed spaces. (ERG, 2024)

Fireproof. Separated from strong oxidants, strong acids, metal oxides, porous materials and food and feedstuffs. Dry. Well closed. Keep under inert gas.

Store in a cool, dry, well-ventilated location. Separate from acids, oxidizing materials, halogens, & air. Outside or detached storage is preferred.

· Wear positive pressure self-contained breathing apparatus (SCBA).

· Wear chemical protective clothing that is specifically recommended by the manufacturer when there is NO RISK OF FIRE.

· Structural firefighters' protective clothing provides thermal protection but only limited chemical protection.

TIH (Toxic Inhalation Hazard) - Term used to describe gases and volatile liquids that are toxic when inhaled. Some are TIH materials themselves, e.g., chlorine, and some release TIH gases when spilled in water, e.g., chlorosilanes. [ERG 2016].

AEGL 1: Notable discomfort, irritation, or certain asymptomatic non-sensory effects. However, the effects are not disabling and are transient and reversible upon cessation of exposure (Unit: ppm)

AEGL 2: Irreversible or other serious, long-lasting adverse health effects or an impaired ability to escape (Unit: ppm)

AEGL 3: Life-threatening health effects or death (Unit: ppm)

NR = Not recommended due to insufficient data

AEGLs Status: Final

0.082 [ppm]

0.90 [ppm]

2.7 [ppm]

0.04 ppm (0.08 mg/m³), [120 minutes]

Ca C 0.04 ppm (0.08 mg/m3) [2-hr] See Appendix A

0.2 ppm (0.35 mg/m³)

C 0.2 ppm (0.35 mg/m3) [skin]

20 ppm ; A potential occupational carcinogen. (NIOSH, 2024)

20.0 [ppm]

Excerpts from Documentation for IDLHs: Basis for original (SCP) IDLH: The chosen IDLH is based on the report by Jacobson et al. [1955] of a mouse LC50 of 56 ppm. . . . Human data: None relevant for use in determining the revised IDLH.

20 ppm; NIOSH considers methyl hydrazine to be a potential occupational carcinogen.

Ca [20 ppm]

See: 60344

0.01 [ppm]

8 hr Time Weighted Avg (TWA): 0.01 ppm, skin.

Excursion Limit Recommendation: Excursions in worker exposure levels may exceed 3 times the TLV-TWA for no more than a total of 30 minutes during a work day, and under no circumstances should they exceed 5 times the TLV-TWA, provided that the TLV-TWA is not exceeded.

A3; Confirmed animal carcinogen with unknown relevance to humans.

0.01 ppm as TWA; (skin); A3 (confirmed animal carcinogen with unknown relevance to humans).

0.01 ppm [1991]

skin absorption (H); sensitization of skin (SH); carcinogen category: 2; germ cell mutagen group: 3B

CAUTION: The majority of these products have a very low flash point. Use of water spray when fighting fire may be inefficient.

CAUTION: Methanol (UN1230) will burn with an invisible flame. Use an alternate method of detection (thermal camera, broom handle, etc.)

Small Fire

· Dry chemical, CO2, water spray or alcohol-resistant foam.

Large Fire

· Water spray, fog or alcohol-resistant foam.

· If it can be done safely, move undamaged containers away from the area around the fire.

· Dike runoff from fire control for later disposal.

· Avoid aiming straight or solid streams directly onto the product.

Fire Involving Tanks, Rail Tank Cars or Highway Tanks

· Fight fire from maximum distance or use unmanned master stream devices or monitor nozzles.

Methylhydrazine appears as a colorless liquid with an ammonia-like odor. Flash point below 75 °F. Spontaneous ignition may occur in contact with oxidizing materials. Very toxic by inhalation and by skin absorption. Produces toxic oxides of nitrogen during combustion. Rate of onset: Immediate Persistence: Hours - days Odor threshold: 1-10 ppm Source/use/other hazard: Solvent, rocket fuel; flammable; irritating to skin/eyes.

Fuming, colorless liquid with an ammonia-like odor; [NIOSH]

COLOURLESS HYGROSCOPIC LIQUID WITH CHARACTERISTIC ODOUR.

Fuming, colorless liquid with an ammonia-like odor.

Clear liquid

Fuming, colorless liquid.

Odor characteristic of short chain, organic amines

Ammonia-like odor

190 °F at 760 mmHg (EPA, 1998)

87.5 °C @760 [mm Hg]

-62.3 °F (EPA, 1998)

-52.4 °C

-62.3 °F

-52.36 °C

158 °F (EPA, 1998)

-8 °C, 17 °F (closed cup)

-8.3 °C c.c.

Insoluble (<1 mg/ml at 75 °F) (NTP, 1992)

>10% in ethyl ether

>10% in ethanol

>10% in water

SOL IN PETROLEUM ETHER

For more Solubility (Complete) data for METHYLHYDRAZINE (6 total), please visit the HSDB record page.

Solubility in water: miscible

Miscible

0.874 at 77 °F (EPA, 1998) - Less dense than water; will float

0.874 at 25 °C

Relative density (water = 1): 0.87

0.874 at 77 °F

0.874 @25 °C

(77 °F): 0.87

1.6 (EPA, 1998) - Heavier than air; will sink (Relative to Air)

1.6 (AIR= 1)

Relative vapor density (air = 1): 1.6

49.6 mmHg at 77 °F (EPA, 1998)

50.0 [mmHg]

50 mm Hg at 25 °C

Vapor pressure, kPa at 20 °C: 4.8

75 [mm Hg] @32.9 °C

log Kow= -1.05

Highly flammable. Often ignites spontaneously. Exposure to air on a large surface may result in spontaneous ignition [Def. Res. and Eng. 27. 1963]. Water soluble. Solutions are highly alkaline and generate heat when water is added.

Azo, Diazo, Azido, Hydrazine, and Azide Compounds

Bases, Weak

Strong Reducing Agent

Pyrophoric

METHYLHYDRAZINE is a powerful reducing agent. Ignites upon contact with oxidizing agents i.e. dinitrogen tetraoxide, hydrogen peroxide [Hawley]. Water used to extinguish a fire may cause pollution and should be diked for later disposal. Gives basic solutions with water that generate heat when water is added.

Reacts violently with oxidizing materials, oxygen, & peroxides; sometimes resulting in autoignition.

Oxides of iron; copper; manganese; lead; copper alloys; porous materials such as earth, asbestos, wood & cloth; strong oxidizers such as fluorine & chlorine; nitric acid; hydrogen peroxide.

Spontaneous ignition may occur if in contact with oxidizing materials.

A powerful reducing agent & fuel, hypergolic with many oxidants such as dinitrogen tetraoxide or hydrogen peroxide.

For more Hazardous Reactivities and Incompatibilities (Complete) data for METHYLHYDRAZINE (6 total), please visit the HSDB record page.

Oxides of iron; copper; manganese; lead; copper alloys; porous materials such as earth, asbestos, wood & cloth; strong oxidizers such as fluorine & chlorine; nitric acid; hydrogen peroxide

A3; Confirmed animal carcinogen with unknown relevance to humans.

At request of the Minister of Social Affairs and Employment, the Health Council of the Netherlands evaluates the carcinogenic properties of substances at the workplace and proposes a classification with reference to the EU-directive. This evaluation is performed by the Dutch Expert Committee on Occupational Standards. The present report contains an evaluation by the committee on the carcinogenicity of N-methylhydrazine. The Committee concludes that N-methylhydrazine should be considered as carcinogenic to humans (comparable with EU-category 2). N-methylhydrazine is genotoxic. Evaluation. No data on humans are available. There is sufficient evidence for the carcinogenicity of N-methylhydrazine in experimental animals. Inhalation of N-methylhydrazine induced benign and malignant tumors in mice and hamsters and oral (drinking water) exposure caused benign tumors in mice and malignant tumors in hamsters in one experiment. No tumors were found in rats and dogs following inhalation, but the exposure time in rats may have been too short, that is 1 year instead of 2 years as recommended in OECD guideline 451. There is some evidence for mutagenic activity in in vitro bacterial systems. No mutations were induced in mammalian cell systems, but chromosome and DNA damage have been found. In vivo, N-methylhydrazine was negative in a dominant lethal assay in rats and mice and in a micronucleus test in dogs. Conflicting results were obtained with respect to DNA damage in liver in vivo assessed with the alkaline elution technique. Recommendation for classification. The committee is of the opinion that N-methylhydrazine should be considered as carcinogenic to humans. It is classified as a genotoxic carcinogen (classification comparable with EU category 2).

The substance can be absorbed into the body by inhalation of its vapour, through the skin and by ingestion.

inhalation, skin absorption, ingestion, skin and/or eye contact

Burning sensation. Cough. Nausea. Vomiting. Blue lips, fingernails and skin. Dizziness. Headache. Shortness of breath. Laboured breathing. Convulsions. Symptoms may be delayed.

MAY BE ABSORBED! Redness. Skin burns. Pain. Further see Inhalation.

Redness. Pain. Severe deep burns.

Abdominal cramps. Burning sensation. Shock or collapse. Further see Inhalation.

irritation eyes, skin, respiratory system; vomiting, diarrhea, tremor, ataxia; anoxia, cyanosis; convulsions; [potential occupational carcinogen]

Eyes, skin, respiratory system, central nervous system, liver, blood, cardiovascular system

[in animals: lung, liver, blood vessel & intestine tumors]

Neurotoxin - Other CNS neurotoxin

Occupational hepatotoxin - Secondary hepatotoxins: the potential for toxic effect in the occupational setting is based on cases of poisoning by human ingestion or animal experimentation.

Methemoglobinemia - The presence of increased methemoglobin in the blood; the compound is classified as secondary toxic effect

Reproductive Toxin - A chemical that is toxic to the reproductive system, including defects in the progeny and injury to male or female reproductive function. Reproductive toxicity includes developmental effects. See Guidelines for Reproductive Toxicity Risk Assessment.

Dermatotoxin - Skin burns.

Toxic Pneumonitis - Inflammation of the lungs induced by inhalation of metal fumes or toxic gases and vapors.

ACGIH Carcinogen - Confirmed Animal.

Methyl Hydrazine

1 x 10^-3 mg/kg-day

PDF Document

Likely to be carcinogenic to humans

SCREEN Current

PPRTV Current

PPRTV Archive

LC50 (rat) = 34 ppm/4 hr

LC50 Rat inhalation 74-78 ppm/4 hr (calculated)

LC50 Mouse inhalation 56-65 ppm/4 hr (calculated)

LC50 Hamster inhalation 143 ppm/4 hr (calculated)

LD50 Mouse intravenous 33 mg/kg

For more Non-Human Toxicity Values (Complete) data for METHYLHYDRAZINE (21 total), please visit the HSDB record page.

Administration of methylhydrazine to mice decreases survival of animals after x-irradiation, inhibited growth of Ehrlich ascites tumor, and increased number of cells with chromosome aberrations.

Methylhydrazine was tested for synergism in promoting in vitro oncogenic transformation of Swiss mouse 3T3 cells by herpes simplex type 2 virus (hsv-2). Methylhydrazine enhanced level of oncogenic transformation approx 2-fold.

Several inhibitors of the FAD-containing monooxygenase (FAD-MO) system from rat liver microsomes (imipramine, chloropromazine, mercaptoethylamine, dithiothreitol, naphthylthiourea, phenylthiocarbamide) and one inhibitor of the liver microsomal cytochrome P450-mediated biotransformations, were tested as possible inhibitors of monomethylhydrazine (MMH) biotransformation to carbon dioxide and to reactive metabolites that bind covalently to nucleic acids and proteins. Results confirm previous suggestions that both FAD-containing monooxygenase system and P450 are involved in monomethylhydrazine metabolism to carbon dioxide and suggest a similar participation of both systems for production of reactive metabolites interacting with macromolecules.

Single sc injections of substituted hydrazines were given alone and jointly with pyridoxine hydrochloride to Swiss mice. The convulsive, toxic and lethal effects of methylhydrazine were successfully prevented by administration of pyridoxine hydrochloride before and/or after injection.

For more Interactions (Complete) data for METHYLHYDRAZINE (7 total), please visit the HSDB record page.

Specific treatment for exposure consists of thorough washing of all exposed skin areas with soap and water, copious irrigation of the eyes, and prompt removal of the patient from the source of exposure. /Hydrazines/

After inhalation, observation for progressive respiratory distress is necessary. Chest X-ray and arterial blood gases should be monitored. Administration of oxygen, intubation, and assisted ventilation may become necessary. Pneumonia and bronchitis need to be excluded. /Hydrazines/

Pyridoxine may be antidotal. Seizures should be controlled with diazepam, phenytoin, or phenobarbital. Blood sugar levels should be monitored for severe hypoglycemia, which may appear with or without preceding significant hyperglycemia. The patient should be observed for evidence of intravascular hemolysis, methemoglobinemia, and consequent deterioration of renal function. Patients who are symptomatic or who demonstrate a methemoglobin level greater than 30 per cent should be treated with methylene blue slowly IV every 4 hours as needed. Improvement is dramatic if diagnosis is correct. Liver function should be monitored because hydrazines are known hepatotoxins. /Hydrazines/

Elimination is enhanced by forced diuresis and acidification of the urine. Hemodialysis and peritoneal dialysis should be effective, but insufficient human data exist on the use of these modalities. Treatment is otherwise symptomatic and supportive. /Hydrazines/

LC50 Hyalella azteca (amphipod) 1.2 mg/L/48 hr /Conditions of bioassay not specified/

LC50 Lebistes reticulatus (Guppy) 5.3; 6.7 mg/L/24 hr; 3.7; 4.0 mg/L/48 hr; 2.7; 3.7 mg/L/72 hr; 2.6; 3.3 mg/L/96 hr; static

LC50 Asellus sp. (Aquatic sowbug) 820 ug/L/48 hr (95% confidence interval: 300-2300 ug/L); static

LC50 Ictalurus punctatus (Channel catfish) 3540 ug/L/96 hr (95% confidence interval: 2510-4970 ug/L); static

For more Ecotoxicity Values (Complete) data for METHYLHYDRAZINE (6 total), please visit the HSDB record page.

1.40e-01

6.20e-01

2.80e-03

1.20e-02

5.60e-03

4.00e+01

1.00e-03

Volatile

1.80e+05

3.10e+00

1.30e+01

6.30e-02

2.60e-01

1.20e-01

The substance is toxic to aquatic organisms.

Methylhydrazine's production and use as a rocket fuel, solvent and chemical intermediate may result in its release to the environment through various waste streams. If released to the atmosphere, methylhydrazine will exist solely in the vapor phase in the ambient atmosphere, based on a measured vapor pressure of 50 mm Hg at 25 °C. Vapor-phase methylhydrazine is degraded in the atmosphere by reaction with photochemically-produced hydroxyl radicals and ozone with estimated half-lives of about 6 hours and 1-12 minutes, respectively. If released to soil, an estimated Koc value of 18 suggests that methylhydrazine will have very high mobility in soil. Methylhydrazine is a weak base having a pKa of 7.87, suggesting that it will partially exist in the protonated form in water and moist soils and the protonated form may adsorb to soils more than the free base. Volatilization from moist soil surfaces will not occur for the protonated species since cations do not volatilize. Volatilization may occur for the neutral species based on an estimated Henry's Law constant of 3X10-6 atm-cu m/mole. The potential for volatilization of methylhydrazine from dry soils may exist based on the vapor pressure of this compound. Based on limited data, methylhydrazine may degrade in soils and water through a combination of biotic and abiotic mechanisms. Approximately 0%, 5%, 20%, and 8% degradation of methylhydrazine was observed in a 1 hour soil column study using a cleaned sand, sandy soil, organic soil and clay soil, respectively. If released to water, the neutral species of methylhydrazine is not expected to adsorb to suspended solids and sediment based on the estimated Koc value; however, the protonated form may have greater adsorption. The protonated form will not volatilize, but the free base may volatilize based on the estimated Henry's Law constant. Volatilization half-lives of 5 and 62 days were estimated for a model river and lake, respectively. Methylhydrazine's degradation in water is catalyzed by metal cations such as Cu(II) and Fe(III) which are common in natural waters. The half-life of methylhydrazine present at 9.5 mM in pond and sea water was 18.0 and 24.1 days, respectively, and at 19.0 mM was 13.1 days in both pond and sea water. An estimated BCF of 3 suggests the potential for bioconcentration in aquatic organisms is low. Occupational exposure may occur through inhalation or dermal contact at workplaces where methylhydrazine is produced or used. Methylhydrazine has been identified as a constituent in the mushroom Gyrimitia esculenta (considered poisonous and probably should not be eaten in most parts of the world), and the general population may be exposed to methylhydrazine through accidental ingestion and through the inhalation of the cooking vapors that are created during the preparation of these mushrooms. (SRC)

Methylhydrazine has been identified as a constituent in the mushroom Gyrimitia esculenta(1-3), considered poisonous and probably should not be eaten in most parts of the world(3).

Methylhydrazine's use in rocket fuel, as an intermediate in chemical synthesis(1) and as a solvent(2), may result in its release to the environment through various waste streams(SRC).

TERRESTRIAL FATE: Based on a classification scheme(1), an estimated Koc value of 18(SRC), determined from a structure estimation method(2), indicates that methylhydrazine is expected to have very high mobility in soil(SRC). Methylhydrazine is a weak base with a pKa of 7.87(3). This pKa value indicates that this compound will partially exist as a cation in moist soils, and cations may adsorb to soil more than neutral compounds(SRC). Volatilization of the protonated species from moist soils will not occur since cations do not volatilize. Volatilization of the free base may occur, based on an estimated Henry's Law constant of 3X10-6 atm-cu m/mole(SRC), calculated from its vapor pressure, 50 mm Hg(4), and water solubility, 1X10+6 mg/L(5). Volatilization from dry soils may occur based on the vapor pressure of this compound(4). Approximately 0%, 5%, 20%, and 8% degradation of methylhydrazine was observed in a 1 hour soil column study using a cleaned sand (100% sand), sandy soil (99.1% sand, 0.4% clay, pH 6.1), organic soil (96.1% sand, 1% clay, 1% carbon, pH 6.4) and clay (69.3% sand, 27.95% clay, pH 3.7)(6).

AQUATIC FATE: Based on a classification scheme(1), an estimated Koc value of 18(SRC), determined from a structure estimation method(2), indicates that methylhydrazine is not expected to adsorb to suspended solids and sediment(SRC). Methylhydrazine is a weak base with a pKa of 7.87(3). This pKa value indicates that this compound will partially exist as a cation in water, and cations may adsorb to suspended solids and sediment more than neutral compounds(SRC). Volatilization of the protonated species will not occur since cations do not volatilize. Volatilization of the free base may occur(4), based on an estimated Henry's Law constant of 3X10-6 atm-cu m/mole(SRC), calculated from its vapor pressure, 50 mm Hg(5), and water solubility, 1X10+6 mg/L(6). Based on this Henry's Law constant, the volatilization half-life from a model river (1 m deep, flowing 1 m/sec, wind velocity of 3 m/sec)(3) is estimated as 5 days(SRC). The volatilization half-life from a model lake (1 m deep, flowing 0.05 m/sec, wind velocity of 0.5 m/sec)(4) is estimated as 62 days(SRC). According to a classification scheme(7), an estimated BCF of 3(SRC), from a log Kow of -1.05(8) and a regression-derived equation(9), suggests the potential for bioconcentration in aquatic organisms is low(SRC). The estimated half-lives of methylhydrazine present at 9.5 mM in pond and sea water are 18.0 and 24.1 days, respectively, and at 19.0 mM are 13.1 days in both pond and sea water(10).

ATMOSPHERIC FATE: According to a model of gas/particle partitioning of semivolatile organic compounds in the atmosphere(1), methylhydrazine, which has a measured vapor pressure of 50 mm Hg at 25 °C(2), will exist solely as a vapor in the ambient atmosphere. Vapor-phase methylhydrazine is degraded in the atmosphere by reaction with photochemically-produced hydroxyl radicals(SRC); the half-life for this reaction in air is estimated to be about 6 hours(SRC) calculated from its rate constant of 6.50X10-11 cu cm/molecule-sec at 25 °C(3). Assuming an ozone concentration of 7X10+11 molecules/cu cm, a maximum half-life of about 3.3 min for the reaction of methylhydrazine with ozone was estimated from a minimum rate constant of 5X10-15 cu cm/molecule sec(4,SRC). The half-life for the reaction between ozone and methylhydrazine was estimated to be <1 min during ozone pollution episodes and <12 min in the 'natural' troposphere(5). Reaction of methylhydrazine with ozone is expected to be the predominant fate of methylhydrazine in the atmosphere(SRC).

The toxicity of methylhydrazine to microbial species was found to be sufficiently high to prevent its degradation by biological waste treatment(1). Large amounts of methylhydrazine, such as might be released from a spill, are not expected to biodegrade. However, biodegradation of lower methylhydrazine concn may occur(SRC). Methylhydrazine at 500 mg/l, present in a wastewater mixture of hydrazine compounds, was incubated with an inoculum prepared from a trickling filter plant; following a 24 hour lag period, this mixture of compounds was biodegraded as measured by oxygen uptake(2). Contaminated wastewater from the NASA Kennedy Space station was studied in batch cultures and trickle bed reactors to monitor the degradation rates of hydrazine containing rocket fuels(3,4). The half-life of methylhydrazine in batch cultures (Rhodococcus B30 or Achromobacter sp.) and trickle bed reactors was about 2.5 and 12 days, respectively(3). Biodegradation may be a significant removal process at low concentrations in soils or ambient waters, but at higher concentrations hydrazines are toxic to microorganisms(4). Concentrations of hydrazine and 1,1-dimethylhydrazine that reduced bacterial metabolism by 50% ranged from 14.6 to 145 mg/L and from 19.2 to 9,060 mg/L, respectively(5).

The rate constant for the vapor-phase reaction of methylhydrazine with photochemically-produced hydroxyl radicals has been measured as 6.50X10-11 cu cm/molecule-sec at 25 °C(1). This corresponds to an atmospheric half-life of about 6 hours at an atmospheric concentration of 5X10+5 hydroxyl radicals per cu cm(1). Dark decay of 11.5 ppm methylhydrazine in a 6400 l chamber at 10% relative humidity (RH) and 24 °C proceeded with a half-life of 19.8 hr(2). Dark decay in a 3800 l chamber of 11.5 ppm methylhydrazine at 10% RH and 24 °C proceeded with a half-life of 49.8 hr and 10.3 ppm methylhydrazine at 17% RH and 22 °C proceeded with a half-life of 30.1 hr(2). The products were ammonia and methyldiazene. Ammonia accounted for only 2% and 4% of the methylhydrazine lost in dry and humidified air, respectively(2). The estimated concentration of methyldiazene in the 3800 l chamber experiments was about 0.3 ppm(2). A minimum reaction rate of about 5X10-15 cu cm/molecule sec was obtained for the reaction between methylhydrazine and ozone in a large chamber with 14-28% RH and from 22-24 °C(2). Assuming an ozone concentration of 7X10+11 molecules/cu cm, the half-life for the reaction of methylhydrazine with ozone is about 3.3 min(SRC). Major products observed were methylhydroperoxide, methyldiazene, formaldehyde, diazomethane and hydrogen peroxide(2). The half-life for the reaction between ozone and methylhydrazine was estimated to be < 1 min during ozone pollution episodes and < 12 min in the 'natural' troposphere(3). The upper limit for the rate of reaction of methylhydrazine with nitrogen dioxide is about 1.4X10-18 cu cm/molecule sec(2). Nitrous oxide does not react significantly with methylhydrazine(2). The lifetime of methylhydrazine in aerosols upon exposure to ozone is about 1 min(4). The aqueous oxidation of methylhydrazine results in methanol, nitromethane and nitrosodimethylamine(4). At a pH of 9.16 and 30 °C, the first order rate constant for the reaction between dissolved oxygen and methylhydrazine is 5.6X10-3 1/min(5) giving a half-life of about 2 hr(SRC).

An estimated BCF value of 3 was calculated for methylhydrazine(SRC), using a measured log Kow of -1.05(1) and a regression-derived equation(2). According to a classification scheme(3), this BCF value suggests that bioconcentration in aquatic organisms is low(SRC).

Using a structure estimation method based on molecular connectivity indices(1), the Koc for methylhydrazine can be estimated to be 18(SRC). According to a classification scheme(2), this estimated Koc value suggests that methylhydrazine is expected to have very high mobility in soil. The pKa of methylhydrazine is 7.87(3). This pKa value indicates that this compound will partially exist as a cation in moist soils and cations generally adsorb more strongly to organic carbon and clay than the corresponding free base(4).

Of the initial amount of methylhydrazine in sand, Vandenburg Air Force Base (VAFB) soil (99.1% sand, 0.4% clay, pH 6.1), organic soil (96.1% sand, 1% clay, 1% carbon, pH 6.4) and clay (69.3% sand, 27.95% clay, pH 3.7), 3%, 46%, 26%, and 64% was adsorbed, respectively(1). Passage of 2 liters of distilled, deionized water through columns containing sand, VAFB soil, organic soil and clay (10% clay plus 90% pure sand) treated with 10 ml of a 0.1 v/v solution of methylhydrazine resulted in 86.9%, 5.5%, 6.5%, 6.3% recovery of methylhydrazine, respectively(1).

1,2-Dimethylhydrazine is a weak base with a pKa of 7.87(1). This value indicates that methylhydrazine will partially exist as a cation in water and moist soil surfaces and cations do not volatilize. The Henry's Law constant for the free base of methylhydrazine is estimated as 3X10-6 atm-cu m/mole(SRC) from its vapor pressure, 50 mm Hg(2), and water solubility, 1X10+6 mg/L(3). Based on this Henry's Law constant, the volatilization half-life from a model river (1 m deep, flowing 1 m/sec, wind velocity of 3 m/sec)(4) is estimated as 5 days (SRC). The volatilization half-life from a model lake (1 m deep, flowing 0.05 m/sec, wind velocity of 0.5 m/sec)(4) is estimated as 62 days(SRC). Methylhydrazine's Henry's Law constant indicates that the free base may volatilize from moist soil surfaces(SRC). The potential for volatilization of methylhydrazine from dry soil surfaces may exist(SRC) based on its vapor pressure(2).

Monomethylhydrazine ... is a decomposition product of the mushroom toxin, gyromitrin (Gyromitra esculenta) ... /when/ generated in vivo is believed to be responsible for the toxicity of gyromitrin.

NIOSH (NOES Survey 1981-1983) has statistically estimated that 1,473 workers (230 of these are female) are potentially exposed to methylhydrazine in the US(1). Methylhydrazine has been identified as a constituent in the mushroom Gyrimitia esculenta (considered poisonous and probably should not be eaten in most parts of the world(4)), and the general population may be exposed to methylhydrazine through accidental ingestion and through inhalation of the cooking vapors that are created during the preparation of these mushrooms(2,3).

Generators of waste (equal to or greater than 100 kg/mo) containing this contaminant, EPA hazardous waste number P068, must conform with USEPA regulations in storage, transportation, treatment and disposal of waste.

Methyl hydrazine is a good candidate for liquid injection incineration with a temperature range of 650 to 1600 °C and a residence time of 0.1 to 2 seconds. Also a good candidate for rotary kiln incineration with a temperature range of 820 to 1,600 °C and residence times of seconds for liquids and gases; for solids hours. Also a good candidate fluidized bed incineration with a temperature range of 450 to 980 °C and residence times of seconds for liquids and gases; longer for solids.

Small Quantities. Wear butyl rubber gloves, laboratory coat and eye prolection. Work in the fume hood. Prepare a dilute (5%) aqueous solution of methylhydrazine by adding slowly to the appropriate volume of water. For each 1 g of methylhydrazine, place 41 ml (about 25% excess) of household laundry bleach (5.25% sodium hypochlorite) into a 3-necked round-bottom flask equipped with a stirrer, thermometer and dropping funnel. Add the aqueous methylhydrazine dropwise to the stirred hypochlorite solution, monitoring the rate of addition by rise in temperature. The temperature is maintained at 45-50 °C and addition takes about 1 hour. Stirring is continued for 2 hours until the temperature gradually falls to room temperature.

Incomplete reaction of hypochlorite with the methylated hydrazine fuels monomethylhydrazine and unsymmetrical dimethylhydrazine leads to a wide variety of byproducts, including N-nitrosoamines, which are believed to be highly carcinogenic.

If ... THERE IS NO FIRE, go directly to the Table of Initial Isolation and Protective Action Distances /(see table below)/ ... to obtain initial isolation and protective action distances. IF THERE IS A FIRE, or IF A FIRE IS INVOLVED, go directly to the appropriate guide /(see guide(s) below)/ and use the evacuation information shown under PUBLIC SAFETY.

Table: Table of Initial Isolation and Protective Action Distances for Methylhydrazine [Table#2950]

/GUIDE 131: FLAMMABLE LIQUIDS - TOXIC/ Fire or Explosion: HIGHLY FLAMMABLE: Will be easily 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 and poison 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.

/GUIDE 131: FLAMMABLE LIQUIDS - TOXIC/ Health: TOXIC; may be fatal if inhaled, ingested or absorbed through skin. Inhalation or contact with some of these materials will irritate or burn 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.

/GUIDE 131: FLAMMABLE LIQUIDS - TOXIC/ Public Safety: CALL Emergency Response Telephone Number on Shipping Paper first. If Shipping Paper not available or no answer, refer to appropriate telephone number listed on the inside back cover. 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.

For more DOT Emergency Guidelines (Complete) data for METHYLHYDRAZINE (9 total), please visit the HSDB record page.

UN 1244; Methylhydrazine

IMO 3.2; Methylhydrazine

49 062 30; Methylhydrazine

No person may /transport,/ offer or accept a hazardous material for transportation in commerce unless that person is registered in conformance ... and the hazardous material is properly classed, described, packaged, marked, labeled, and in condition for shipment as required or authorized by ... /the hazardous materials regulations (49 CFR 171-177)./

The International Air Transport Association (IATA) Dangerous Goods Regulations are published by the IATA Dangerous Goods Board pursuant to IATA Resolutions 618 and 619 and constitute a manual of industry carrier regulations to be followed by all IATA Member airlines when transporting hazardous materials.

The International Maritime Dangerous Goods Code lays down basic principles for transporting hazardous chemicals. Detailed recommendations for individual substances and a number of recommendations for good practice are included in the classes dealing with such substances. A general index of technical names has also been compiled. This index should always be consulted when attempting to locate the appropriate procedures to be used when shipping any substance or article.

Poison Inhalation Hazard Flammable Liquid Corrosive

Unbreakable packaging. Put breakable packaging into closed unbreakable container. Do not transport with food and feedstuffs.

UN Hazard Class: 6.1; UN Subsidiary Risks: 3 and 8; UN Pack Group: I