Phosphine

H220: Extremely flammable gas [Danger Flammable gases]

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

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

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

P203, P210, P222, P260, P264, P271, P273, P280, P284, P301+P330+P331, P302+P361+P354, P304+P340, P305+P354+P338, P316, P320, P321, P363, P377, P381, P391, P403, P403+P233, P405, and P501 (click each P-code to see the statement)

H220 (100%): Extremely flammable gas [Danger Flammable gases]

H280 (64.9%): Contains gas under pressure; may explode if heated [Warning Gases under pressure]

H314 (100%): Causes severe skin burns and eye damage [Danger Skin corrosion/irritation]

H330 (100%): Fatal if inhaled [Danger Acute toxicity, inhalation]

H400 (100%): Very toxic to aquatic life [Warning Hazardous to the aquatic environment, acute hazard]

P203, P210, P222, P260, P264, P271, P273, P280, P284, P301+P330+P331, P302+P361+P354, P304+P340, P305+P354+P338, P316, P320, P321, P363, P377, P381, P391, P403, P403+P233, P405, P410+P403, and P501 (click each P-code to see the statement)

Aggregated GHS information provided per 202 reports by companies from 8 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.

Not Classified

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

P203, P210, P222, P260, P264, P270, P271, P280, P284, P304+P340, P308+P316, P316, P320, P321, P377, P381, P403, P403+P233, P405, and P501 (click each P-code to see the statement)

P203, P210, P222, P280, P377, P381, and P403 (click each P-code to see the statement)

H280: Contains gas under pressure; may explode if heated [Warning Gases under pressure]

P203, P210, P222, P260, P264, P270, P271, P280, P284, P304+P340, P308+P316, P316, P320, P321, P377, P381, P403, P403+P233, P405, P410+P403, and P501 (click each P-code to see the statement)

H318: Causes serious eye damage [Danger Serious eye damage/eye irritation]

P203, P210, P222, P260, P264, P264+P265, P271, P273, P280, P284, P301+P330+P331, P302+P361+P354, P304+P340, P305+P354+P338, P316, P317, P320, P321, P363, P377, P381, P391, P403, P403+P233, P405, P410+P403, and P501 (click each P-code to see the statement)

Fresh air, rest. Half-upright position. Administration of oxygen may be needed. Artificial respiration may be needed. Refer immediately for medical attention.

ON FROSTBITE: rinse with plenty of water, do NOT remove clothes. Refer for medical attention .

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

Warning: Effects may be delayed for several hours. Caution is advised.

Signs and Symptoms of Acute Phosphine Exposure: Acute exposure to phosphine usually results in headache, cough, tightness and pain in the chest, shortness of breath, dizziness, lethargy, and stupor. Fatigue, muscle pain, chills, tremors, incoordination, seizures, and coma may be seen. Pulmonary edema and cardiac arrhythmias are common. Gastrointestinal symptoms include nausea, vomiting, abdominal pain, and diarrhea. Renal (kidney) damage, hepatic (liver) damage, and jaundice may also occur. Contact with phosphine may burn the skin and eyes.

Emergency Life-Support Procedures: Acute exposure to phosphine 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 phosphine.

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. Transport to a health care facility.

Dermal/Eye Exposure:

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

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 twice 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. Transport to a health care facility.

Ingestion Exposure: No information is available. (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.

· Keep victim calm and warm.

· Keep victim under observation.

· For further assistance, contact your local Poison Control Center.

· Note: Basic Life Support (BLS) and Advanced Life Support (ALS) should be done by trained professionals.

Specific First Aid:

· In case of contact with liquefied gas, only medical personnel should attempt thawing frosted parts.

· In case of burns, immediately cool affected skin for as long as possible with cold water. Do not remove clothing if adhering to skin.

Wear full protective clothing including self-contained breathing apparatus, rubber gloves, boots, and bands around legs, arms, and waist. No skin surface should be exposed. For massive fires in cargo areas, use unmanned hose holders or monitor nozzles. Move containers from fire area.

If material is on fire or involved in a fire, do not extinguish 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, carbon dioxide or dry chemical. (EPA, 1998)

Shut off supply; if not possible and no risk to surroundings, let the fire burn itself out. In other cases extinguish with powder, carbon dioxide. In case of fire: keep cylinder cool by spraying with water. Combat fire from a sheltered position.

- Phosphine is extremely flammable and explosive.

- The agent may ignite spontaneously on contact with air.

- The agent may be ignited by heat, sparks, or flames.

- When phosphine burns, it produces a dense white cloud of a severe respiratory irritant (phosphorus pentoxide).

- Vapors may travel to the source of ignition and flash back.

- Run-off may create a fire hazard.

- Do not extinguish a leaking gas fire unless the leak can be stopped.

- For small fires, use dry chemical, carbon dioxide, water spray, or alcohol-resistant foam.

- For large fires, use water spray, fog, or alcohol-resistant foam. Move containers from the fire area if it is possible to do so without risk to personnel. Damaged cylinders should be handled only by specialists.

- For fire involving tanks, fight the fire from maximum distance or use unmanned hose holders or monitor nozzles. Cool containers with flooding quantities of water until well after the fire is out. Do not direct water at the source of the leak or at safety devices; icing may occur. Withdraw immediately in case of rising sound from venting safety devices or discoloration of tanks. Always stay away from tanks engulfed in fire.

- Run-off from fire control may cause pollution.

- If the situation allows, control and properly dispose of run-off (effluent).

Suitable extinguishing media: Use water spray, alcohol-resistant foam, dry chemical or carbon dioxide.

Advice for firefighters: Wear self-contained breathing apparatus for firefighting if necessary.

Use water spray to cool unopened containers.

To fight fire, use /carbon dioxide/, dry chemical, or water spray.

For more Fire Fighting Procedures (Complete) data for Phosphine (7 total), please visit the HSDB record page.

Evolves hydrogen and ignites on contact with many materials. Vapors are heavier than air and may travel to a source of ignition and flash back. Closed containers may rupture violently when heated.

· 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.

· Many gases are heavier than air and will spread along the ground and collect in low or confined areas (sewers, basements, tanks, etc.).

· 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.

· Do not direct water at spill or source of leak.

· Use water spray to reduce vapors or divert vapor cloud drift. Avoid allowing water runoff to contact spilled material.

· FOR CHLOROSILANES, use alcohol-resistant foam to reduce vapors.

· If possible, turn leaking containers so that gas escapes rather than liquid.

· Prevent entry into waterways, sewers, basements or confined areas.

· Isolate area until gas has dispersed.

Excerpt from ERG Guide 119 [Gases - Toxic - Flammable]:

IMMEDIATE PRECAUTIONARY MEASURE: Isolate spill or leak area for at least 100 meters (330 feet) in all directions.

SPILL: See ERG Table 1 - Initial Isolation and Protective Action Distances on the UN/NA 2199 datasheet.

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

Immediate precautionary measure

· Isolate spill or leak area for at least 100 meters (330 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 1600 meters (1 mile) in all directions; also, consider initial evacuation for 1600 meters (1 mile) in all directions.

Small spill:

- ISOLATE in all directions: 60 m (200 ft)

Large spill:

- ISOLATE in all directions: 400 m (1250 ft)

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

- PROTECT people from downwind during NIGHT time: 1.1 km (0.7 mi)

- PROTECT people from downwind during DAY time: 1.3 km (0.8 mi)

- PROTECT people from downwind during NIGHT time: 3.7 km (2.3 mi)

Evacuate danger area! Consult an expert! Ventilation. Personal protection: chemical protection suit including self-contained breathing apparatus.

ACCIDENTAL RELEASE MEASURES: Personal precautions, protective equipment and emergency procedures: Wear respiratory protection. Avoid breathing vapors, mist or gas. Ensure adequate ventilation. Remove all sources of ignition. Evacuate personnel to safe areas. Beware of vapors accumulating to form explosive concentrations. Vapors can accumulate in low areas. Environmental precautions: Prevent further leakage or spillage if safe to do so. Do not let product enter drains. Discharge into the environment must be avoided. Methods and materials for containment and cleaning up: Clean up promptly by sweeping or vacuum.

Arsine and phosphine were removed from waste gases of semiconductor manufacture by ozone oxidation and carbon adsorption.

Porous supports (pearlite or aluminum oxide) impregnated with aqueous silver nitrate, or with aqueous ferric chloride containing other metal salts are used for purging of phosphine in waste gas from a semiconductor plant.

Poisonous gases, including phosphine, are diluted with nitrogen or neon and injected into an aqueous foaming agent, preferably under paraffin.

Wear special protective clothing and positive pressure self-contained breathing apparatus. ... Stop or control the leak, if this can be done without undue risk. Use water spray to cool and disperse vapors and protect personnel. Approach release from upwind.

Generators of waste (equal to or greater than 100 kg/mo) containing this contaminant, EPA hazardous waste number P096, must conform with USEPA regulations in storage, transportation, treatment and disposal of waste.

SRP: Wastewater from contaminant suppression, cleaning of protective clothing/equipment, or contaminated sites should be contained and evaluated for subject chemical or decomposition product concentrations. Concentrations shall be lower than applicable environmental discharge or disposal criteria. Alternatively, pretreatment and/or discharge to a permitted wastewater treatment facility is acceptable only after review by the governing authority and assurance that "pass through" violations will not occur. Due consideration shall be given to remediation worker exposure (inhalation, dermal and ingestion) as well as fate during treatment, transfer and disposal. If it is not practicable to manage the chemical in this fashion, it must be evaluated in accordance with EPA 40 CFR Part 261, specifically Subpart B, in order to determine the appropriate local, state and federal requirements for disposal.

Excerpt from ERG Guide 119 [Gases - Toxic - Flammable]:

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. Do not direct water at spill or source of leak. Use water spray to reduce vapors or divert vapor cloud drift. Avoid allowing water runoff to contact spilled material. FOR CHLOROSILANES, use alcohol-resistant foam to reduce vapors. If possible, turn leaking containers so that gas escapes rather than liquid. Prevent entry into waterways, sewers, basements or confined areas. Isolate area until gas has dispersed. (ERG, 2024)

Fireproof. Keep in a well-ventilated room.

Keep container tightly closed in a dry and well-ventilated place. Contents under pressure. Storage class (TRGS 510): Gases.

Store in a cool, dry, well-ventilated location. Separate from acids, alkalies, and halogenated compounds. 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].

0.1 [ppm]

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)

AEGLs Status: Final

0.15 [ppm]

2.0 [ppm]

3.6 [ppm]

0.3 ppm (0.4 mg/m³)

1 ppm (1 mg/m³)

TWA 0.3 ppm (0.4 mg/m3) ST 1 ppm (1 mg/m3)

0.3 [ppm]

TWA 0.3 ppm (0.4 mg/m3) See Appendix G

50 ppm (NIOSH, 2024)

50.0 [ppm]

Excerpts from Documentation for IDLHs: Symptoms such as diarrhea, nausea and vomiting, tightness of the chest, cough, headache, and dizziness have been reported in workers exposed intermittently to concentrations up to 35 ppm [Jones et al. 1964]. It has been stated that 290 to 430 ppm is dangerous to life after 1 hour, and 100 to 200 ppm is the maximum amount for 0.5 to 1 hour [Henderson and Haggard 1943].

See: 7803512

0.05 [ppm]

8 hr Time Weighted Avg (TWA): 0.3 ppm; 15 min Short Term Exposure Limit (STEL): 1 ppm.

2017 Notice of Intended Changes (NIC): These substances, with their corresponding values and notations, comprise those for which (1) a limit is proposed for the first time, (2) a change in the Adopted value is proposed, (3) retention as an NIC is proposed, or (4) withdrawal of the Documentation and adopted TLV is proposed. In each case, the proposals should be considered trial values during the period they are on the NIC. These proposals were ratified by the ACGIH Board of Directors and will remain on the NIC for approximately one year following this ratification. If the Committee neither finds nor receives any substantive data that changes its scientific opinion regarding an NIC TLV, the Committee may then approve its recommendation to the ACGIH Board of Directors for adoption. If the Committee finds or receives substantive data that change its scientific opinion regarding an NIC TLV, the Committee may change its recommendation to the ACGIH Board of Directors for the matter to be either retained on or withdrawn from the NIC. Substance: Phosphine; Time Weighted Avg (TWA): 0.05 ppm; Short Term Exposure Limit (STEL): Ceiling limit: 0.15 ppm; Notations: A4: Not classifiable as a human carcinogen.; Molecular Weight: 34.00; TLV Basis: Respiratory tract irritation; lung edema, cardiac toxicity.

0.05 ppm as TWA; (ceiling value): 0.15 ppm as STEL; A4 (not classifiable as a human carcinogen).

0.05 ppm [2017]

0.15 ppm [2017]

0.14 mg/m

· DO NOT EXTINGUISH A LEAKING GAS FIRE UNLESS LEAK CAN BE STOPPED.

Small Fire

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

Large Fire

· Water spray, fog or alcohol-resistant foam.

· FOR CHLOROSILANES, DO NOT USE WATER; use alcohol-resistant foam.

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

· Damaged cylinders should be handled only by specialists.

Fire Involving Tanks

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

Phosphine appears as a colorless gas with a disagreeable odor of fish or garlic. Boiling point -126 °F; freezing point -209 °F. Very toxic by inhalation at extremely low concentrations. Prolonged heating may cause containers to rupture violently and rocket. Rate of onset: Immediate & Delayed (Lungs) Persistence: Minutes - hours Odor threshold: 0.9 ppm Source/use/other hazard: Insecticide; used in manufacture of flame retardants and incendiaries.

CBI; Gas Vapor

Colorless gas with a fish- or garlic-like odor. [pesticide] [Note: Shipped as a liquefied compressed gas. Pure compound is odorless.] [NIOSH] Vapor density = 1.17 (heavier than air); [Burke, p. 102]

COLOURLESS COMPRESSED LIQUEFIED GAS.

Colorless gas with a fish- or garlic-like odor.

Colorless gas with a fish- or garlic-like odor. [pesticide] [Note: Shipped as a liquefied compressed gas. Pure compound is odorless.]

Colorless gas.

Colorless gas; flammable

Colorless gas [Note: Shipped as a liquefied compressed gas].

Disagreeable, garlic-like odor.

Almost odorless in purest form, but odor of decaying fish when occurring industrially.

Foul odor of decaying fish

Fish- or garlic-like odor [Note: Pure compound is odorless].

-126 °F at 760 mmHg (EPA, 1998)

-87.75 °C

-87.7 °C

-87.75 °C @760 [mm Hg]

-207 °F (EPA, 1998)

-133.8 °C

-132.5 °C

Flammable gas

NA (Gas)

Slight (NIOSH, 2024)

Slightly soluble in water (0.26 volume at 20 °C)

Insoluble in water

Slightly soluble in cold water. Insoluble in hot water.

Soluble in alcohol, ether, and cuprous chloride solution

Slightly soluble in ethanol, ether

Solubility in water, ml/100ml at 17 °C: 26 (very poor)

0.746 at -130 °F (EPA, 1998) - Less dense than water; will float

1.390 g/L at 25 °C

Density: 1.529 g/L at 0 °C

Density (gas): 1.53 kg/m³

Relative density (water = 1): 0.8

0.746 at -130 °F

1.39 @25 °C

1.18(relative gas density)

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

1.17 (Air = 1)

Relative vapor density (air = 1): 1.18

Highly flammable. Usually ignites spontaneously in air. Burns with a luminous flame [Merck 11th ed. 1989]. Insoluble in water.

Amines, Phosphines, and Pyridines

Reducing Agents, Strong

Strong Reducing Agent

Pyrophoric

CSL00177

Phosphine (PH3) + Oxygen

Phosphine reacted with air resulting in an explosion

Explosive

Not Available

User Reported

04/22/2022

04/21/2022

PHOSPHINE is a reducing agent. Ignites spontaneously in air when pure [Sidgwick, 1950, p. 729]. Liquefied phosphine can be detonated [Rust, 1948, p. 301]. Ignites or reacts violently with boron trichloride, dichlorine oxide, halogens (bromine, chlorine, iodine), metal nitrates, nitrogen oxides, nitric acid, nitrous acid, nitrogen trichloride [Bretherick, 5th ed., 1995, p. 1562]. Forms explosive mixtures with even small amounts of oxygen. Autoignites at low pressures [Fisher, E. O. et al., Angew. Chem., 1968, 7, p. 136].

Incompatible materials: Strong oxidizing agents, oxidizing agents, halogens, nitric acid.

Combines violently with oxygen and the halogens. Liberates hydrogen and forms the phosphide when passed over heated metal. Forms phosphonium salts when brought in contact with the halogen acids.

Explosive reaction with dichlorine oxide, silver nitrate, concentrated nitric acid, nitrogen trichloride, oxygen. Reacts with mercury(II) nitrate to form an explosive product. Ignition or violent reaction with air, boron trichloride, /bromine/, /chlorine/ aqueous halogen solutions, iodine, metal nitrates, /nitric oxide, nitrogen trichloride, nitrate, nitrous oxide, nitrous acid, potassium + ammonia/, oxidants. The organic derivatives of phosphine (phosphines) react vigorously with halogens.

Air, oxidizers, chlorine, acids, moisture, halogenated hydrocarbons, copper [Note: May ignite SPONTANEOUSLY on contact with air].

For more Hazardous Reactivities and Incompatibilities (Complete) data for Phosphine (25 total), please visit the HSDB record page.

Air, oxidizers, chlorine, acids, moisture, halogenated hydrocarbons, copper [Note: May ignite SPONTANEOUSLY on contact with air.]

IDENTIFICATION AND USE: Phosphine is a colorless gas with a garlic-like odor. Phosphine is a fumigant, used indoors to control a broad spectrum of insects for non-food/non-feed commodities in sealed containers or structures. It is also used as a doping agent for electronic components, in chemical synthesis, and as an intermediate for the preparation of several flame retardants. HUMAN STUDIES: Direct contact with phosphine liquid may cause frostbite. Toxic exposures to phosphine have been documented as a result of grain fumigation, attempted suicide, and ferrosilicon decomposition. Potential symptoms of overexposure are nausea, vomiting, abdominal pain, diarrhea, thirst, chest tightness, dyspnea, muscle pain, chills, stupor or syncope, and pulmonary edema. A productive cough with fluorescent green sputum, acute dyspnea, and pulmonary edema may develop. Death may be preceded by tonic convulsions, which may ensue after apparent recovery. Death may occur after 1/2 to 1 hr of exposure at concentrations of 400 to 600 ppm. Serious effects may be produced by exposure to 5 to 10 ppm for several hours. Main histopathologic findings of fatal phosphine poisoning in the liver are fine cytoplasmic vacuolization of hepatocytes and sinusoidal congestion. Fumigant applicators had significantly increased stable chromosome rearrangements, primarily translocations in G-banded lymphocytes. Less stable aberrations included chromatid deletions and gaps but these were significantly increased only during the application season, and not at later time points. Exposure of human lymphocytes to phosphine (1.4 to 4.5 ug/L) for 20 mins yielded increased chromosome aberrations after 96 hr of lymphocyte culture, indicating that the expression of genotoxicity of phosphine is delayed. ANIMAL STUDIES: In rats, signs of exposure were typical of respiratory irritation and included hyperemia of the ears, salivation, lacrimation, face-pawing, and dyspnea. Rats exposed to phosphine repeatedly at 4 ppm for 4 hours daily on 9 of 12 days exhibited a slightly reduced weight gain, which returned to normal during the 14-day recovery period. Signs of mild respiratory irritation were observed in these animals. One study of animal teratogenicity with exposure as high as 4.9 ppm during days 6 to 15 of gestation in rats showed neither maternal toxicity nor developmental toxicity. In an in vitro cytogenetic assay with Chinese hamster ovary (CHO) cells, phosphine was positive at 2500 and 5000 ppm without metabolic activation. This resulted in a significant, but not dose-related increase in the frequency of cells with structural chromosome aberrations. Significant clastogenic effects were also noted at 2500 ppm with metabolic activation, but not at the highest dose tested (5000 ppm). Increased micronucleus (MN) induction in bone marrow polychromatic erythrocytes (PCE) was seen following subchronic exposure to phosphine in male mice at 5.0 ppm, and female mice at 2.5 and 5.0 ppm. In rats, MN elevation in bone marrow PCE and pulmonary alveolar macrophages was seen at 1.0 and 4.0 ppm, respectively, following subchronic exposure. ECOTOXICITY STUDIES: Three turkeys were exposed to phosphine at a concentration of 211 mg/cu m and 6 hens at 224 mg/cu m in an acute inhalation study. The turkeys exhibited apathy, restlessness, dyspnea, and tonic-clonic convulsions, and died after 68, 74, and 80 min, respectively. Hens exhibited tonic-clonic convulsions and died after an average of 59 min. Their organs were also congested with oxygenated blood. In rice seeds, phosphine has inhibitory effects on seed germination. In addition, phosphine exposure caused oxidative stress in the seeds.

Phosphine inhibits cytochrome c oxidase, preventing mitochondrial oxidative phosphorylation. This non-competitive inhibition prevents cellular respiration and leads to multi-organ dysfunction. Phosphine can also react with hydrogen peroxide to form the highly reactive hydroxyl radical, which can cause lipid peroxidation. (A291, A292)

Phosphine

3 x 10 ^-4 mg/kg-day

3 x 10 ^-4 mg/m^3

CLASSIFICATION: D; not classifiable as to human carcinogenicity. BASIS FOR CLASSIFICATION: Based on inadequate data in animals and no tumor data in humans. While phospine has not been associated with cancer in humans, there is some evidence of chromosomal damage (transient chromatid deletions, gaps and breaks, persistent chromosomal translocations). A relationship between these genetic effects and the development of cancer in humans is sometimes postulated. HUMAN CARCINOGENICITY DATA: None. ANIMAL CARCINOGENICITY DATA: Inadequate.

No indication of carcinogenicity to humans (not listed by IARC).

Inhalation of phosphine may cause severe pulmonary irritation leading to acute pulmonary oedema, cardiovascular dysfunction, CNS excitation, coma and death. Gastrointestinal disorders, renal damage and leukopenia may also occur. Chronic exposure to phosphine can result in anemia, bronchitis, gastrointestinal effects, and visual, speech and motor problems. (L980, L982)

The substance can be absorbed into the body by inhalation.

inhalation, skin and/or eye contact (liquid)

Phosphine can be absorbed into the body by inhalation. Direct contact with phosphine liquid may cause frostbite.

Oral (L1645) ; inhalation (L1645) ; dermal (L1645)

Headache. Dizziness. Nausea. Diarrhoea. Chest pain. Shortness of breath. Irregular heartbeat. Convulsions. Unconsciousness.

ON CONTACT WITH LIQUID: FROSTBITE.

nausea, vomiting, abdominal pain, diarrhea; thirst; chest tightness, dyspnea (breathing difficulty); muscle pain, chills; stupor or syncope; pulmonary edema; liquid: frostbite

- Phosphine gas produces no known adverse effects on the eyes.

- Ocular exposure to phosphine gas has not been known to cause systemic toxicity.

- Direct eye contact with liquefied or compressed phosphine gas, which is unlikely, may cause frostbite.

- Phosphine is present as a gas at room temperature, so ingestion is unlikely.

- See Inhalation Exposure.

- Mild to moderate: Severe lung irritation; chest tightness or burning chest pain; cough, sometimes productive of fluorescent green sputum; difficulty breathing or shortness of breath (dyspnea); and accumulation of fluid in the lungs (pulmonary edema). Cardiovascular effects include abnormally low blood pressure (hypotension), irregular heart rhythm (dysrhythmia), and decreased ability of the heart to pump a normal blood volume. Nervous system effects include headache, restlessness, irritability, dizziness, lethargy, drowsiness, fatigue, loss of feeling, impaired gait, trembling of the extremities during movement, and double vision. Gastrointestinal effects include nausea, vomiting (emesis), diarrhea, abdominal pain, gastrointestinal distress, and liver injury. General effects include sweating and bluish discoloration of the skin (cyanosis).

- Severe: Death. Lung effects include accumulation of fluid in the lungs (pulmonary edema). Cardiovascular effects include abnormally low blood pressure (hypotension); abnormally rapid heart rate (tachycardia); collapse of blood vessels (peripheral vascular collapse) not responsive to drug therapy; abnormal, life-threatening heart rhythms (ventricular dysrhythmias); cardiac arrest; and critically low blood pressure (shock). Nervous system effects include seizures and prolonged loss of consciousness (coma).

- Phosphine gas is not known to produce adverse effects on the skin.

- Contact with the skin does not normally result in whole-body (systemic) toxicity.

- Skin contact with liquefied or compressed phosphine gas may cause frostbite.

Early symptoms of acute phosphine intoxication include pain in the diaphragm, nausea, vomiting, excitement, and a phosphorus smell on the breath. Higher levels can cause weakness, bronchitis, pulmonary edema, shortness of breath, convulsions, and death. Some effects, such as pulmonary edema, convulsions, and liver injury, may appear or continue to be present days after an exposure. Liquid phosphine on your skin can cause frostbite. Ingestion of metal phosphides results in release of phosphine in your stomach which can cause nausea, vomiting, abdominal pain, and diarrhea. (L980)

respiratory system

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.

Nephrotoxin - The chemical is potentially toxic to the kidneys in the occupational setting.

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

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

ACGIH Carcinogen - Not Classifiable.

IRIS Current

HEAST Current

LC50 (rat) = 11 ppm/4H

LC50: 11 ppm over 4 hours (Inhalation, Rat) (T80)

Three ppm safe for long term exposure, 500 ppm lethal in 30 min. 1000 ppm lethal after few breaths (for man). In phosphine inhalation, survival for 4 days is ordinarily followed by recovery.... .

LC50 Rat (male) inhalation 11 ppm/4 hr

LC50 Rat (male) inhalation 0.44 umol/L/4 hr.

/BIRDS and MAMMALS/ Three turkeys /were exposed/ to phosphine at a concentration of 211 mg/cu m and 6 hens at 224 mg/cu m in an acute inhalation study. The turkeys exhibited apathy, restlessness, dyspnea, and tonic-clonic convulsions, and died after 68, 74, and 80 min, respectively. When examined, organs were congested with oxygenated blood. Hens exhibited tonic-clonic convulsions and died after an average of 59 min (range, 50-64 min). Their organs were also congested with oxygenated blood.

/PLANTS/ Ambient levels of phosphine (PH3) in the air, phosphine emission fluxes from paddy fields and rice plants, and the distribution of matrix-bound phosphine (MBP) in paddy soils were investigated throughout the growing stages of rice. The relationships between MBP and environmental factors were analyzed to identify the principal factors determining the distribution of MBP. The phosphine ambient levels ranged from 2.368 +/- 0.6060 ng/cu m to 24.83 +/- 6.529 ng/cu m and averaged 14.25 +/- 4.547 ng/cu m. The highest phosphine emission flux was 22.54 +/- 3.897 ng/sq m/hr, the lowest flux was 7.64 +/- 4.83 ng/sq m/hr, and the average flux was 14.17 +/- 4.977 ng/sq m/hr. Rice plants transport a significant portion of the phosphine emitted from the paddy fields. The highest contribution rate of rice plants to the phosphine emission fluxes reached 73.73% and the average contribution was 43.00%. The average MBP content of 111.6 ng/kg fluctuated significantly in different stages of rice growth and initially increased then decreased with increasing depth. The peak MBP content in each growth stage occurred approximately 10 cm under the surface of paddy soils. Pearson correlation analyses and stepwise multiple regression analysis showed that soil temperature (Ts), acid phosphatase (ACP) and total phosphorus (TP) were the principal environmental factors, with correlative rankings of Ts>ACP>TP.

/PLANTS/ Rice seeds (Tianyou, 3618) were used to examine the physiological and biochemical responses to phosphine exposure during germination. A control (0 mg/cu m) and four concentrations of phosphine (1.4 mg/cu m, 4.2 mg/cu m, 7.0 mg/cu m and 13.9 mg/cu m) were used to treat the rice seeds. Each treatment was applied for 90 min once per day for five days. The germination rate (GR); germination potential (GP); germination index (GI); antioxidant enzymes, including superoxide dismutase (SOD), peroxidase (POD), and catalase (CAT); and lipid peroxidation measured through via malondialdehyde (MDA) were determined as indicators of the physiological and biochemical responses of the rice seeds to phosphine exposure. These indicators were determined once per day for five days. The results indicated that the GR, GP and GI of the rice seeds markedly decreased after phosphine exposure. The changes in the activities of the antioxidant enzymes due to the phosphine exposure were also significant. The exposure lowered the CAT and SOD activities and increased POD activity in the treated rice seeds compared with controls. The MDA content exhibited a slow increase trend with the increase of phosphine concentration. These results suggest that phosphine has inhibitory effects on seed germination. In addition, phosphine exposure caused oxidative stress in the seeds. The antioxidant enzymes could play a pivotal role against oxidative injury. Overall, the effect of phosphine on rice seeds is different from what has been reported previously for insects and mammals.

2.30e+01

3.50e+02

3.10e-01

1.30e+00

5.70e-01

1.5E+01(G)

3.00e-04

Volatile

7.00e+01

1.10e+03

9.40e-01

3.90e+00

1.70e+00

1.5E+01 (G)

This substance does enter the environment under normal use. Great care, however, should be taken to avoid any additional release, for example through inappropriate disposal.

Phosphine's production as a by-product from the storage of ferrous alloys and phosphide hydrolysis may result in its release to the environment through various waste streams. Phosphine's use as an insecticide or rodenticide will result in its direct release to the environment. Phosphine is formed when other fumigants (aluminum phosphide, magnesium phosphide, calcium phosphide, zinc phosphide) degrade. Phosphine gas is produced in the degradation of phosphate containing organic sources and can be generated in sediments, soils, sludge and water. If released to air, phosphine will be degraded in the atmosphere by reaction with photochemically-produced hydroxyl radicals; and has a reported atmospheric half-life of 5 hours. Phosphine will dissipate rapidly from soil and water surfaces. Studies have shown that sub-surface phosphine may bind to soil. Occupational exposure to phosphine may occur through inhalation and dermal contact with this compound at workplaces where phosphine is produced or used. Monitoring and use data indicate that the general population is not expected to be exposed to phosphine. (SRC)

Phosphine gas is produced in the degradation of phosphate containing organic sources and can be generated in sediments, soils, sludge, animal waste and water(1-3).

Phosphine's production as a by-product from the storage of ferrous alloys and phosphide hydrolysis(1) may result in its release to the environment through various waste streams(SRC). Phosphine's use as an insecticide or rodenticide(2) will result in its direct release to the environment(SRC). Phosphine is formed when other fumigants (aluminum phosphide, magnesium phosphide, calcium phosphide, zinc phosphide) degrade(2).

TERRESTRIAL FATE: Phosphine is a gas(1) and, therefore, is expected to dissipate rapidly from both moist and dry soil(SRC). Studies have shown that sub-surface phosphine may bind to soil(2-3).

TERRESTRIAL FATE: The sorption and desorption of phosphine from wheat treated with a concentration of 0.5-5 mg/kg wheat were determined at 25, 45, and 85 °C. The desorbed phosphine was extracted from the air by passing through a cold trap. Most of the phosphine was desorbed in the first 2-3 days but small amounts continued to desorb for many weeks following treatment. After 220 days of aeration, phosphine was still present and desorbing. Even when the temp was increased to 85 °C for several days, unreacted phosphine still desorbed slowly from wheat. Corn aerated 26 days desorbed 0.004 ng/g in 2 days.

AQUATIC FATE: Phosphine is a gas and, therefore, is expected to dissipate rapidly from water surfaces(1). Biodegradation, hydrolysis and bioconcentration are not expected to be important fate processes when compared to dissipation(SRC).

ATMOSPHERIC FATE: Phosphine is a gas at ambient temperature(1). Gas-phase phosphine is degraded in the atmosphere by reaction with photochemically-produced hydroxyl radicals and has a reported atmospheric half-life of 5 hours(2).

Degradation of phosphine in the atmosphere is expected to predominately occur via photochemically-produced hydroxyl radicals with a reported half-life of less than one day(1). The half-life in air is approximately 5 hours with expected degradation products being oxyacids of phosphorus and inorganic phosphate(2).

Phosphine is a gas(1) and may bind to soil(2). Laboratory studies suggest that phosphine present below the soil surface is quickly adsorbed, but interaction with soil is soil-type dependent(3).

Phosphine is a gas under normal environmental conditions and will dissipate rapidly from water and soil surfaces(1).

SEDIMENT: Matrix-bound phosphine was detected in sediment samples from paddy fields and reservoirs in Beijing, China at the following concentrations(1):[Table#3036]

URBAN/SUBURBAN: Phosphine levels in Beijing, China typically were at their highest in the morning and overall were lower during the spring and winter time(1).[Table#3015]

RURAL/REMOTE: Phosphine was detected in two of eight samples collected Dec 2005 over the southern ocean at 1.32 and 147.9 ng/cu m. Phosphine was detected in samples collected Dec 23, 2005 to Feb 17, 2006 at eight other coastal locations of Antarctica at 30.0-271.8 ng/cu m(1).

SOURCE DOMINATED: Phosphine was detected at 26-41, 127-135 and 32-1062 ng/cu m in gas samples taken in Beijing from a paddy field (marsh gas), a water reservoir (marsh gas) and a landfill (landfill gas), respectively. In ambient air samples near these locations, phosphine was detected at 127-146, 50-166, and 1-71 ng/cu m, respectively(1).

SOURCE DOMINATED: The ambient level of phosphine and emission fluxes measured over rice paddies throughout growing stages were reported as 2.368-24.83 ng/cu m and 7.64-22.54 ng/sq m-hr, respectively(1). Approximate values for each stage were as follows(1):[Table#3016]

SOURCE DOMINATED: The concentration and flux of phosphine was measured in atmospheric samples collected Dec 23, 2005 to Feb 17, 2006 from penguin colonies from the Antarctic biosphere as follows(1):[Table#3017]

Occupational exposure to phosphine may occur through inhalation and dermal contact with this compound at workplaces where phosphine is produced or used. Monitoring and use data indicate that the general population is not expected to be exposed to phosphine. (SRC)

Generators of waste (equal to or greater than 100 kg/mo) containing this contaminant, EPA hazardous waste number P096, must conform with USEPA regulations in storage, transportation, treatment and disposal of waste.

SRP: Wastewater from contaminant suppression, cleaning of protective clothing/equipment, or contaminated sites should be contained and evaluated for subject chemical or decomposition product concentrations. Concentrations shall be lower than applicable environmental discharge or disposal criteria. Alternatively, pretreatment and/or discharge to a permitted wastewater treatment facility is acceptable only after review by the governing authority and assurance that "pass through" violations will not occur. Due consideration shall be given to remediation worker exposure (inhalation, dermal and ingestion) as well as fate during treatment, transfer and disposal. If it is not practicable to manage the chemical in this fashion, it must be evaluated in accordance with EPA 40 CFR Part 261, specifically Subpart B, in order to determine the appropriate local, state and federal requirements for disposal.

Product: Contact a licensed professional waste disposal service to dispose of this material. Burn in a chemical incinerator equipped with an afterburner and scrubber but exert extra care in igniting as this material is highly flammable. Offer surplus and non-recyclable solutions to a licensed disposal company; Contaminated packaging: Dispose of as unused product.

A potential candidate for rotary kiln incineration at a temperature range of 820 to 1,600 °C and residence times of seconds for liquids and gases, and hours for solids. A potential candidate for fluidized bed incineration at a temperature range of 450 to 980 °C and residence times of seconds for liquids and gases, and longer for solids.

Surplus gas or leaking cylinder can be vented slowly to air in a safe, open area or gas burnt off through a suitable burner in a fume cupboard. Recommendable methods: Evaporation & open burning. Not recommendable method: Landfill. Peer-review: Dilute with much air prior to evaporation. Care: Highly toxic gas, may be spontaneously flammable in air. (Peer-review conclusions of an IRPTC expert consultation (May 1985))

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 Phosphine ID: 2199 [Table#3022]

/GUIDE 119 GASES - TOXIC - FLAMMABLE/ Fire or Explosion: Flammable; may be ignited by heat, sparks or flames. May form explosive mixtures with air. Those substances designated with a (P) may polymerize explosively when heated or involved in a fire. 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 toxic and flammable gas through pressure relief devices. Containers may explode when heated. Ruptured cylinders may rocket. Runoff may create fire or explosion hazard.

/GUIDE 119 GASES - TOXIC - FLAMMABLE/ Health: TOXIC; may be fatal if inhaled or absorbed through skin. 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.

/GUIDE 119 GASES - TOXIC - FLAMMABLE/ 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 100 meters (330 feet) in all directions. Keep unauthorized personnel away. Stay upwind, uphill and/or upstream. Many gases are heavier than air and will spread along ground and collect in low or confined areas (sewers, basements, tanks). Ventilate closed spaces before entering.

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

UN 2199; Phosphine

IMO 2.3; Phosphine

49 201 60; Phosphine

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. Phosphine is included on the dangerous goods list.

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. Phosphine is included on the dangerous goods list.

Poison Gas Flammable Gas

Symbol: F+, T+, N; R: 12-17-26-34-50; S: (1/2)-28-36/37-45-61-63

UN Hazard Class: 2.3; UN Subsidiary Risks: 2.1