Propargyl bromide

Wear self-contained breathing apparatus and full protective clothing. Move container from fire area if you can do it without risk. Do not get water inside container. Cool containers that are exposed to flames with water from the side until well after fire is out. Withdraw immediately in case of rising sound from venting safety device or any discoloration of tank due to fire. Isolate for 1/2 mile in all directions if tank car or truck is involved in fire.

· 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.

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

Warning: Propargyl bromide is very toxic via the oral route, has corrosive effects, causes burns to skin and eyes, and is a strong lacrimating agent.

General First Aid:

Fire Fighting Procedure: Use water spray, dry chemical, foam, or carbon dioxide. Use fine spray or fog to control fire by preventing its spread and absorbing some of its heat. Application of a water blanket may be effective for extinguishment. 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.

If material on fire or involved in fire: Do not extinguish fire unless flow can be stopped. Use water in flooding quantities as fog. Solid streams of water may be ineffective. Cool all affected containers with flooding quantities of water. Use alcohol foam, dry chemical or carbon dioxide. Keep run-off water out of sewers and water sources.

Unstabilized material should be stored like an explosive. If diluted, material should be stored like a flammable material. Store in a cool, dry, well-ventilated location. Outside or detached storage is preferred. Separate from oxidizing materials. Inside storage should be in a standard flammable liquids storage warehouse, room, or cabinet.

Absorb the spill with paper towels. ... Place in hood to evaporate material.

Spill or leak procedures: Eliminate all ignition sources. Stop or control the leak, if this can be done without undue risk. Use water spray to cool and disperse vapors, and protect personnel. Control runoff and isolate discharged material for proper disposal. Fire situations may require evacuation.

Dissolve in a combustible solvent. Scatter spray of solution into a furnace with afterburner and alkali scrubber.

SRP: At the time of review, criteria for land treatment or burial (sanitary landfill) disposal practices are subject to significant revision. Prior to implementing land disposal of waste residue (including waste sludge), consult with environmental regulatory agencies for guidance on acceptable disposal practices.

If material on fire or involved in fire: Do not extinguish fire unless flow can be stopped. Use water in flooding quantities as fog. Solid streams of water may be ineffective. Cool all affected containers with flooding quantities of water. Use alcohol foam, dry chemical or carbon dioxide. Keep run-off water out of sewers and water sources.

Personnel protection: Avoid breathing vapors. Keep upwind. Do not handle broken packages unless wearing appropriate personal protective equipment. If contact with the material anticipated, wear appropriate chemical protective clothing.

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 130 [Flammable Liquids (Water-Immiscible / Noxious)]:

Immediate precautionary measure

Tolerances are established for residues of inorganic bromides (calculated as Br) in or on the following raw agricultural commodities grown in soil fumigated with combinations of chloropicrin, methyl bromide, and propargyl bromide. No tolerances are established for chloropicrin since it has been established that no residue of this substance remains in the raw agricultural commodity: broccoli, 25 ppm; cauliflower, 25 ppm; eggplant, 60 ppm; muskmelon, 40 ppm; pepper, 25 ppm; pineapple, 25 ppm; strawberry, 25 ppm; and tomato 40 ppm.

Tolerances with regional registration, as defined in §180.1(n), are established for residues of inorganic bromides (calculated as Br) in or on the following raw agricultural commodities grown in soil fumigated with combinations of chloropicrin, methyl bromide, and propargyl bromide: asparagus, 300 ppm; lettuce, 300 ppm; and onion, dry bulb, 300 ppm.

TERRESTRIAL FATE: Based on a classification scheme(1), Koc values of 1.1 and 5.3(2) indicate that 3-bromo-1-propyne is expected to have very high mobility in soil(SRC). Volatilization of 3-bromo-1-propyne from moist soil surfaces is expected to be an important fate process(SRC) given a Henry's Law constant of 1.13X10-3 atm-cu m/mole(2). 3-Bromo-1-propyne is expected to volatilize from dry soil surfaces(SRC) based upon an estimated vapor pressure of 108 mm Hg(SRC), calculated using a water solubility of 1.49X10+4 mg/L(2) and the Henry's Law constant(2). Biodegradation in soil is not expected to compete with chemical degradation processes based on similar half-lives in sterile soil (0.37-11 days) and nonsterile soil (0.046-12 days)(2,3,4). It has been proposed that the alkylation of soil organic matter is the primary degradation process for 3-bromo-1-propyne in soil(2-4).

TERRESTRIAL FATE: The measured first-order degradation rate constants for 310 mg/kg 3-bromo-1-propyne in autoclaved Arlington sand loam, nonautoclaved Arlington sand loam, autoclaved Linne clay loam, and nonautoclaved Linne clay loam were 0.065, 0.056, 0.20, and 0.20 per day, respectively, which correspond to half-lives of 11, 12, 3.5, and 3.5 days, respectively(1). The measured first-order degradation rate constants for 20 mg/kg 3-bromo-1-propyne in sterile Arlington sandy loam, Carsitas loamy sand, and Linne clay loam were 0.18, 0.57, and 0.39 per day, respectively, which correspond to half-lives of 3.9, 1.2, and 1.8 days, respectively(2). Measured rate constants for this substance (20 mg/kg) in nonsterile Arlington sandy loam, Carsitas loamy sand, and Linne clay loam were 0.14, 0.46, and 0.48 per day, respectively, which correspond to half-lives of 5.0, 1.5, and 1.4 days, respectively(2). Half-lives determined from first-order degradation rate constants for 0.7 mg/kg 3-bromo-1-propyne in sterile Coachella fine sand, Arlington sandy loam, Chualar loam, and Florida muck were 2.4, 2.4, 1.0, and 0.37 days, respectively at an inital concentration of 0.7 mg/kg; 3.2, 4.6, 3.0, and 0.71 days, respectively at an initial concentration of 7 mg/kg; and 6.3, 6.9, 3.5, and 1.2 days, respectively at an initial concentration of 70 mg/kg(3). Half-lives determined from first-order degradation rate constants for 0.7 mg/kg propargyl bromide in non-sterile Coachella fine sand, Arlington sandy loam, Chualar loam, and Florida muck were 3.5, 0.39, 0.36, and 0.046 days, respectively at an inital concentration of 0.7 mg/kg; 4.1, 3.6, 2.8, and 0.43 days, respectively at an initial concentration of 7 mg/kg; and 8.7, 7.7, 4.6, and 1.1 days, respectively at an initial concentration of 70 mg/kg(3).

AQUATIC FATE: Based on a classification scheme(1), Koc values of 1.1 and 5.3(2), indicate that 3-bromo-1-propyne is not expected to adsorb to suspended solids and sediment(SRC). Volatilization from water surfaces is expected(3) based upon a Henry's Law constant of 1.13X10-3 atm-cu m/mole(2). Using this Henry's Law constant and an estimation method(3), volatilization half-lives for a model river and model lake are 2 hours and 5 days, respectively(SRC). According to a classification scheme(4), an estimated BCF of 3(SRC), from a water solubility of 1.49X10+4 mg/L(2) and a regression-derived equation(5), suggests the potential for bioconcentration in aquatic organisms is low(SRC). 3-Bromo-1-propyne is expected to undergo hydrolysis based on measured half-lives of 64 and 47 days at 22 and 25 °C, respectively(2,6). Biodegradation in water is not expected to compete with chemical degradation processes based on similar half-lives in sterile soil (0.37-11 days) and nonsterile soil (0.046-12 days)(2,6,7).

ATMOSPHERIC FATE: According to a model of gas/particle partitioning of semivolatile organic compounds in the atmosphere(1), 3-bromo-1-propyne, which has an estimated vapor pressure of 108 mm Hg at 25 °C(SRC), calculated from a water solubility of 1.49X10+4 mg/L(2) and a Henry's Law constant of 1.13X10-3 atm-cu m/mol(2), is expected to exist solely as a vapor in the ambient atmosphere. Vapor-phase 3-bromo-1-propyne 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 3 days(SRC), calculated from its rate constant of 5.6X10-12 cu cm/molecule-sec at 25 °C(SRC) that was derived using a structure estimation method(3). Propargyl bromide does not contain chromophores that absorb at wavelengths >290 nm and therefore is not expected to be susceptible to direct photolysis by sunlight(SRC).

Koc values of 1.1 and 5.3 were determined for 3-bromo-1-propyne in Linne clay loam (Kd = 0.033, 2.99% organic matter) and Arlington sandy loam (Kd = 0.049, 0.93% organic matter), respectively(1). According to a classification scheme(2), these Koc values suggest that 3-bromo-1-propyne is expected to have very high mobility in soil.

3-Bromopropyne (CAS # 106-96-7) was evaluated for acute oral toxicity. The test substance was administer by oral gavage to rats (dosage, sex, number of rats, and strain was not reported). The LD50 was determined to be 0.067 g/kg. No further information was submitted.

3-Bromopropyne (CAS # 106-96-7) was evaluated for acute oral toxicity. The test substance was administer by oral gavage to guinea pigs (dosage, sex, number of guinea pigs, and strain was not reported). The LD50 was determined to be 0.029 g/kg. No further information was submitted.

3-Bromopropyne (CAS # 106-96-7) was evaluated for acute inhalation toxicity. Number of rats and strain were not reported. All of the rats exposed to 1000 ppm for 1 hour, 200 ppm for 4 hours, and 120 ppm for 7 hours died. All rats exposed to 1000 ppm for 0.2 hours, 200 ppm for 0.5 hours, and 120 ppm for 2 hours survived. Vapor inhalation of test substance is considered irritating and under the above conditions caused slight liver and kidney injury. No further information was submitted.

/SIGNS AND SYMPTOMS/ Symptomatology: 1. A. Inhalation, high vapor concn: gasping, refusal to breathe, coughing, substernal pain, and extreme respiratory distress at vapor concn over 1500 ppm. Irritation of eyes and upper respiratory mucosa appears promptly after exposure to concentrated vapors. Lacrimation and headache are prominent. Coma may occur rapidly. B. Inhalation, low vapor concentrations: Central nervous depression and moderate irritation of respiratory system. Headache is frequent. /Dichloropropenes/

/SIGNS AND SYMPTOMS/ Symptomatology: 2. Dermal: Severe skin irritation with marked inflammatory response of epidermis and underlying tissues. 3. Oral: Acute gastrointestinal distress with pulmonary congestion and edema. Central nervous depression, perhaps even in the absence of impaired oxygen uptake. 4. By any route, possible late injuries to liver, kidneys and heart. 5. After inhalation exposures, malaise, headache, chest and abdominal discomfort and irritability have been reported to persist for several years. /Dichloropropenes/

/SIGNS AND SYMPTOMS/ Vapors and liquid are corrosive toward skin, eyes, and mucous membranes.

/Propargyl bromide/ vapors are very toxic.

3-Bromo-1-propyne's production and use as a chemical intermediate(1) may result in its release to the environment through various waste streams; its former production and use as a soil fumigant(1) may have resulted in its direct release to the environment(SRC).

An estimated BCF of 3 was calculated for 3-bromo-1-propyne(SRC), using a water solubility of 1.49X10+4 mg/L(1) and a regression-derived equation(2). According to a classification scheme(3), this BCF suggests the potential for bioconcentration in aquatic organisms is low(SRC).

The Henry's Law constant for 3-bromo-1-propyne is 1.13X10-3 atm-cu m/mole(1). This Henry's Law constant indicates that 3-bromo-1-propyne is expected to volatilize rapidly from water surfaces(2). 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)(2) is estimated as 2 hours(SRC). The volatilization half-life from a model lake (1 m deep, flowing 0.05 m/sec, wind velocity of 0.5 m/sec)(2) is estimated as 5 days(SRC). 3-Bromo-1-propyne's Henry's Law constant indicates that volatilization from moist soil surfaces may occur(SRC). 3-Bromo-1-propyne is expected to volatilize from dry soil surfaces(SRC) based upon an estimated vapor pressure of 108 mm Hg(SRC), calculated using a water solubility of 1.49X10+4 mg/L(2) and its Henry's Law constant(2).

The rate constant for the vapor-phase reaction of 3-bromo-1-propyne with photochemically-produced hydroxyl radicals has been estimated as 5.6X10-12 cu cm/molecule-sec at 25 °C(SRC) using a structure estimation method(1). This corresponds to an atmospheric half-life of about 3 days at an atmospheric concentration of 5X10+5 hydroxyl radicals per cu cm(1). A hydrolysis half-life of 47 days at 25 °C was calculated for 3-bromo-1-propyne using a rate constant (not reported) determined from measurements at temperatures between 2 and 40 °C(2). A hydrolysis half-life of 64 days at 22 °C has also been measured for this substance(3). The hydrolysis products observed during this reaction were propargyl hydroxide and bromide ion(3). 3-Bromo-1-propyne does not contain chromophores that absorb at wavelengths >290 nm and therefore is not expected to be susceptible to direct photolysis by sunlight(SRC).

The measured first-order degradation rate constants for 310 mg/kg propargyl bromide in autoclaved Arlington sand loam and Linne clay loam were 0.065 and 0.20 per day, respectively, which correspond to half-lives of 11 and 3.5 days, respectively(1). The measured first-order degradation rate constants for 20 mg/kg 3-bromo-1-propyne in sterile Arlington sandy loam, Carsitas loamy sand, and Linne clay loam were 0.18, 0.57, and 0.39 per day, respectively, which correspond to half-lives of 3.9, 1.2, and 1.8 days, respectively(2). Half-lives determined from first-order degradation rate constants for 0.7 mg/kg 3-bromo-1-propyne in sterile Coachella fine sand, Arlington sandy loam, Chualar loam, and Florida muck were 2.4, 2.4, 1.0, and 0.37 days, respectively at an inital concentration of 0.7 mg/kg; 3.2, 4.6, 3.0, and 0.71 days, respectively at an initial concentration of 7 mg/kg; and 6.3, 6.9, 3.5, and 1.2 days, respectively at an initial concentration of 70 mg/kg(3). It has been proposed that the primary degradation process for 3-bromo-1-propyne in soil is the alkylation of soil organic matter(1-3).

Tolerances are established for residues of inorganic bromides (calculated as Br) in or on the following raw agricultural commodities grown in soil fumigated with combinations of chloropicrin, methyl bromide, and propargyl bromide. No tolerances are established for chloropicrin since it has been established that no residue of this substance remains in the raw agricultural commodity: broccoli; cauliflower; eggplant; muskmelon; pepper; pineapple; strawberry; and tomato.

Tolerances with regional registration, as defined in §180.1(n), are established for residues of inorganic bromides (calculated as Br) in or on the following raw agricultural commodities grown in soil fumigated with combinations of chloropicrin, methyl bromide, and propargyl bromide: asparagus; lettuce; and onion, dry bulb.

Releases of CERCLA hazardous substances are subject to the release reporting requirement of CERCLA section 103, codified at 40 CFR part 302, in addition to the requirements of 40 CFR part 355. Propargyl bromide is an extremely hazardous substance (EHS) subject to reporting requirements when stored in amounts in excess of its threshold planning quantity (TPQ) of 10 lbs.