METHYL BROMIDE

Methyl bromide is a halogenated aliphatic hydrocarbon used in ionization chambers, for degreasing wool, extracting oils from flowers, nuts, and seeds, and as an insect fumigant for freight cars, mills, ships (naval shipping cargo holds), soil, vaults, and warehouses (Breeman, 2009; Bingham et al, 2001; Budavari, 1996). It has commonly been used in the food industry as a fumigant for insect control because it diffuses readily into all nooks and small spaces, is very effective at killing pests, and leaves no residue on food products (EPA, 1988).
Methyl bromide is also used as a methylating agent and a chemical intermediate, as a low-boiling solvent in aniline dye manufacture, as an intermediate in drug manufacturing (Bingham et al, 2001; Sittig, 1991). It is used as a fungicide, herbicide, nematocide, rodenticide, and insecticide (Bingham et al, 2001). It is used on agricultural crops; stored commodities; ornamentals; for soil, manure, mulch, and compost fumigation; in greenhouses, homes, grain elevators, mills, ships, and transportation vehicles (EPA, 1988). It is used to treat potatoes, tomatoes, and other crops (Lewis, 1993). It is used against fruit flies in citrus fruit shipments (Lewis, 1998).
"Because of its toxicity, there has been considerable concern against distributing this gas in small fire extinguishers" (Budavari, 1996). ACGIH (1991) reports that methyl bromide is no longer used as a refrigerant or as a fire extinguisher because of high incidence of injury and death. Since methyl bromide is odorless, it is often "stenched" with chloropicrin (0.25% and 2.0%) as a warning agent in all formulations, except those used for commodity fumigation (Bingham et al, 2001; EPA, 1988). Chloropicrin causes painful irritation to the eyes and has a disagreeable pungent odor (at low concentrations) (EPA, 1988). Chloropicrin vapor may disappear before the methyl bromide vapor and therefore may not serve as a reliable warning device (Clayton & Clayton, 1994).
Methyl bromide was traditionally used in fire extinguishers in aircraft engines and in submarines during World War II. It has been used as a refrigerant (Behrens & Dukes, 1986).
PESTICIDE

Since methyl bromide damages the ozone layer, the Declaration of Montreal was signed in January 2005 to prohibit the use of methyl bromide in the European Union (Breeman, 2009). However, it is still being used in many countries (eg, New Zealand) (Bulathsinghala & Shaw, 2014). In the United States, the use of methyl bromide is banned in homes and other residential locations. In March 2015, 4 family members (2 adults and 2 teens; age range, 14 to 49 years) who were vacationing in the US Virgin islands, presented with acute methyl bromide toxicity 2 days after a condominium below their unit was fumigated with methyl bromide. In addition, 37 patients were exposed to methyl bromide in the same condominium complex (Kulkarni et al, 2015).

FORMS

Methyl bromide takes the form of a colorless, transparent, volatile liquid or gas with a burning taste (Breeman, 2009; Bingham et al, 2001; HSDB , 2001). It is nearly odorless except at high concentrations where it has a chloroform odor. Due to its high olfactory threshold, it often provides little warning of its presence. Chloropicrin is typically added to commercial forms of methyl bromide to give it an intense odor. Because its vapor density is greater than that of air, it tends to accumulate near the floor or ground (Bingham et al, 2001; HSDB , 2001).
Methyl bromide is supplied in cylinders of compressed gas and small bombs for treatment of storage spaces.

SOURCES

Methyl bromide is synthesized industrially by the action of hydrobromic acid on methanol. In one modification of this process, sulfuric acid is added to sodium bromide and methanol, then methyl bromide is removed by distillation (Budavari, 1996).

-CLINICAL EFFECTS

GENERAL CLINICAL EFFECTS

USES: Methyl bromide is used in ionization chambers, for degreasing wool, extracting oils from flowers, nuts, and seeds, and as an insect fumigant for freight cars, mills, ships (naval shipping cargo holds), soil, vaults, and warehouses. It has commonly been used in the food industry as a fumigant for insect control.

TOXICOLOGY: Methyl bromide, a halogenated aliphatic hydrocarbon, is an odorless, colorless liquid or gas at ambient temperatures. At low vapor concentrations, methyl bromide is not detectable by odor, but can still have serious toxic effects. Methyl bromide may be mixed with a strong-smelling irritant, chloropicrin, to provide warning of exposure, although dangerous levels can exist without warning. The unique characteristic of the low molecular weight halocarbons (and other fumigant gases) is their capacity to penetrate coverings and tissues, including rubber protective gear, fabrics, neoprene, skin, and mucous membranes. Dermal penetration is so efficient that exposed workers have been poisoned even when wearing an effective self-contained breathing apparatus. BROMISM VS METHYL BROMIDE TOXICITY: The exact mechanism of methyl bromide-induced CNS toxicity is still unclear. Several sources reported that methyl bromide acts directly as an alkylating agent on amino acids and bioactive proteins with sulfhydryl groups, resulting in a permanent cytotoxic effects. However, bromide ions temporarily displace chloride ions in neuronal cells resulting in impaired neurotransmission. Serum bromide concentration is poorly correlated with toxic effects of methyl bromide. S-METHYLCYSTEINE: In studies of humans and animals exposed to methyl bromide, s-methylcysteine, which is produced by a reaction between methyl bromide and cysteine, was detected in the circulatory systems. S-methylcysteine may be neurotoxic because of its structural analogy with gamma-aminobutanoic acid (GABA) and possible interactions with GABA receptors.

EPIDEMIOLOGY: Exposure is rare.

WITH POISONING/EXPOSURE

Methyl bromide is an eye, skin, and mucus membrane irritant. Absorption occurs readily through the lungs and to a lesser extent through the skin. Onset of toxicity may be delayed several hours, and may be limited to headache, nausea, vomiting, and visual changes. Dermal contact with the liquid can cause a tingling or burning sensation, itching, redness, and swelling; contact with large amounts may cause numbness or aching pain, blisters, papules, vesicles, or chemical burns. Other signs and symptoms may include blurred or double vision, nystagmus, cough, tachypnea, cyanosis, lethargy, profound weakness, dizziness, slurring of speech, hyperreflexia, albuminuria, hematuria, oliguria, anuria, impaired liver function, memory loss, confusion, delirium, euphoria, disorientation, agitation, and hallucinations.
At high airborne concentrations, pneumonitis, pulmonary edema, intracranial hemorrhage, hypotension, dysrhythmias, paralysis, seizures, and coma may occur. Metabolic acidosis has been reported in patients with methyl bromide-induced seizures or myoclonus. Central and peripheral neurologic sequelae such as organic brain syndrome and extrapyramidal effects have also been reported. If coma and seizures occur, few patients survive. Death may occur in a few days due to circulatory failure or pulmonary edema and multiple organ failure. In nonfatal cases, complete recovery may take several months. Neuropsychiatric sequelae may persist indefinitely.

POTENTIAL HEALTH HAZARDS - EMERGENCY RESPONSE GUIDEBOOK, GUIDE 123 (ERG, 2004)

TOXIC; may be fatal if inhaled or absorbed through skin.
Vapors may be irritating.
Contact with gas or liquefied gas may cause burns, severe injury and/or frostbite.
Fire will produce irritating, corrosive and/or toxic gases.
Runoff from fire control may cause pollution.

-FIRST AID

FIRST AID AND PREHOSPITAL TREATMENT

SUMMARY

As methyl bromide is a gas at ambient temperatures, ingestion exposure is unlikely. Ingestion of liquid methyl bromide may result in burns of the oropharynx. Prehospital gastrointestinal decontamination is generally not recommended because of the potential for CNS depression or persistent seizures and subsequent aspiration.

INHALATION

Move patient from the toxic environment to fresh air. Monitor for respiratory distress. If cough or difficulty in breathing develops, evaluate for hypoxia, respiratory tract irritation, bronchitis, or pneumonitis.
OBSERVATION: Carefully observe patients with inhalation exposure for the development of any systemic signs or symptoms and administer symptomatic treatment as necessary.
INITIAL TREATMENT: Administer 100% humidified supplemental oxygen, perform endotracheal intubation and provide assisted ventilation as required. Administer inhaled beta-2 adrenergic agonists, if bronchospasm develops. Consider systemic corticosteroids in patients with significant bronchospasm (National Heart,Lung,and Blood Institute, 2007). Exposed skin and eyes should be flushed with copious amounts of water.

DERMAL

DECONTAMINATION: Remove contaminated clothing and jewelry and place them in plastic bags. Wash exposed areas with soap and water for 10 to 15 minutes with gentle sponging to avoid skin breakdown. Rescue personnel and bystanders should avoid direct contact with contaminated skin, clothing, or other objects (Burgess et al, 1999). Since contaminated leather items cannot be decontaminated, they should be discarded (Simpson & Schuman, 2002).

EYE IRRIGATION, ROUTINE: Remove contact lenses and irrigate exposed eyes with copious amounts of room temperature 0.9% saline or water for at least 15 minutes. If irritation, pain, swelling, lacrimation, or photophobia persist after 15 minutes of irrigation, an ophthalmologic examination should be performed (Peate, 2007; Naradzay & Barish, 2006).

-MEDICAL TREATMENT

LIFE SUPPORT

Support respiratory and cardiovascular function.

SUMMARY

FIRST AID - EMERGENCY RESPONSE GUIDEBOOK, GUIDE 123 (ERG, 2004)

Move victim to fresh air.
Call 911 or emergency medical service.
Give artificial respiration if victim is not breathing.
Do not use mouth-to-mouth method if victim ingested or inhaled the substance; give artificial respiration with the aid of a pocket mask equipped with a one-way valve or other proper respiratory medical device.
Administer oxygen if breathing is difficult.
Remove and isolate contaminated clothing and shoes.
In case of contact with liquefied gas, thaw frosted parts with lukewarm water.
In case of contact with substance, immediately flush skin or eyes with running water for at least 20 minutes.
Keep victim warm and quiet.
Keep victim under observation.
Effects of contact or inhalation may be delayed.
Ensure that medical personnel are aware of the material(s) involved and take precautions to protect themselves.

FIRST AID

FIRST AID

EYE EXPOSURE (liquid): Immediately wash the eyes with large amounts of water, occasionally lifting the lower and upper lids. Get medical attention immediately. Contact lenses should not be worn when working with this chemical.
DERMAL EXPOSURE (liquid): Immediately flush the contaminated skin with water. If this chemical penetrates the clothing, immediately remove the clothing and flush the skin with water. Get medical attention promptly.
INHALATION EXPOSURE: Move the exposed person to fresh air at once. If breathing has stopped, perform artificial respiration. Keep the affected person warm and at rest. Get medical attention as soon as possible.
TARGET ORGANS: Eyes, skin, respiratory system, and central nervous system (National Institute for Occupational Safety and Health, 2007).

INHALATION EXPOSURE

INHALATION: Move patient to fresh air. Monitor for respiratory distress. If cough or difficulty breathing develops, evaluate for respiratory tract irritation, bronchitis, or pneumonitis. Administer oxygen and assist ventilation as required. Treat bronchospasm with an inhaled beta2-adrenergic agonist. Consider systemic corticosteroids in patients with significant bronchospasm.
BRONCHOSPASM SUMMARY

Administer beta2 adrenergic agonists. Consider use of inhaled ipratropium and systemic corticosteroids. Monitor peak expiratory flow rate, monitor for hypoxia and respiratory failure, and administer oxygen as necessary.

ALBUTEROL/ADULT DOSE

2.5 to 5 milligrams diluted with 4 milliliters of 0.9% saline by nebulizer every 20 minutes for three doses. If incomplete response, administer 2.5 to 10 milligrams every 1 to 4 hours as needed OR administer 10 to 15 milligrams every hour by continuous nebulizer as needed. Consider adding ipratropium to the nebulized albuterol; DOSE: 0.5 milligram by nebulizer every 30 minutes for three doses then every 2 to 4 hours as needed, NOT administered as a single agent (National Heart,Lung,and Blood Institute, 2007).

ALBUTEROL/PEDIATRIC DOSE

0.15 milligram/kilogram (minimum 2.5 milligrams) diluted with 4 milliliters of 0.9% saline by nebulizer every 20 minutes for three doses. If incomplete response administer 0.15 to 0.3 milligram/kilogram (maximum 10 milligrams) every 1 to 4 hours as needed OR administer 0.5 mg/kg/hr by continuous nebulizer as needed. Consider adding ipratropium to the nebulized albuterol; DOSE: 0.25 to 0.5 milligram by nebulizer every 20 minutes for three doses then every 2 to 4 hours as needed, NOT administered as a single agent (National Heart,Lung,and Blood Institute, 2007).

ALBUTEROL/CAUTIONS

The incidence of adverse effects of beta2-agonists may be increased in older patients, particularly those with pre-existing ischemic heart disease (National Asthma Education and Prevention Program, 2007). Monitor for tachycardia, tremors.

CORTICOSTEROIDS

Consider systemic corticosteroids in patients with significant bronchospasm. PREDNISONE: ADULT: 40 to 80 milligrams/day in 1 or 2 divided doses. CHILD: 1 to 2 milligrams/kilogram/day (maximum 60 mg) in 1 or 2 divided doses (National Heart,Lung,and Blood Institute, 2007).

ACUTE LUNG INJURY: Maintain ventilation and oxygenation and evaluate with frequent arterial blood gases and/or pulse oximetry monitoring. Early use of PEEP and mechanical ventilation may be needed.
SEIZURES: Administer a benzodiazepine; DIAZEPAM (ADULT: 5 to 10 mg IV initially; repeat every 5 to 20 minutes as needed. CHILD: 0.1 to 0.5 mg/kg IV over 2 to 5 minutes; up to a maximum of 10 mg/dose. May repeat dose every 5 to 10 minutes as needed) or LORAZEPAM (ADULT: 2 to 4 mg IV initially; repeat every 5 to 10 minutes as needed, if seizures persist. CHILD: 0.05 to 0.1 mg/kg IV over 2 to 5 minutes, up to a maximum of 4 mg/dose; may repeat in 5 to 15 minutes as needed, if seizures continue).

Consider phenobarbital or propofol if seizures recur after diazepam 30 mg (adults) or 10 mg (children greater than 5 years).
Monitor for hypotension, dysrhythmias, respiratory depression, and need for endotracheal intubation. Evaluate for hypoglycemia, electrolyte disturbances, and hypoxia.

Carefully observe patients with inhalation exposure for the development of any systemic signs or symptoms and administer symptomatic treatment as necessary.

DERMAL EXPOSURE

DECONTAMINATION: Remove contaminated clothing and jewelry and place them in plastic bags. Wash exposed areas with soap and water for 10 to 15 minutes with gentle sponging to avoid skin breakdown. A physician may need to examine the area if irritation or pain persists (Burgess et al, 1999).
Treat dermal irritation or burns with standard topical therapy. Patients developing dermal hypersensitivity reactions may require treatment with systemic or topical corticosteroids or antihistamines.
Some chemicals can produce systemic poisoning by absorption through intact skin. Carefully observe patients with dermal exposure for the development of any systemic signs or symptoms and administer symptomatic treatment as necessary.

EYE EXPOSURE

DECONTAMINATION: Remove contact lenses and irrigate exposed eyes with copious amounts of room temperature 0.9% saline or water for at least 15 minutes. If irritation, pain, swelling, lacrimation, or photophobia persist after 15 minutes of irrigation, the patient should be seen in a healthcare facility.

ORAL EXPOSURE

As methyl bromide is a gas at ambient temperatures, ingestion exposure is unlikely. Ingestion of methyl bromide may result in burns of the oropharynx. Prehospital gastrointestinal decontamination is generally not recommended because of the potential for CNS depression or persistent seizures and subsequent aspiration.
Significant esophageal or gastrointestinal tract irritation or burns may occur following ingestion. The possible benefit of early removal of some ingested material by cautious gastric lavage must be weighed against potential complications of bleeding or perforation.
CORROSIVE INGESTION/SUMMARY: The use of corticosteroids for the treatment of caustic ingestion is controversial. Most animal studies have involved alkali-induced injury (Haller & Bachman, 1964; Saedi et al, 1973). Most human studies have been retrospective and generally involve more alkali than acid-induced injury and small numbers of patients with documented second or third degree mucosal injury.
FIRST DEGREE BURNS: These burns generally heal well and rarely result in stricture formation (Zargar et al, 1989; Howell et al, 1992). Corticosteroids are generally not beneficial in these patients (Howell et al, 1992).
SECOND DEGREE BURNS: Some authors recommend corticosteroid treatment to prevent stricture formation in patients with a second degree, deep-partial thickness burn (Howell et al, 1992). However, no well controlled human study has documented efficacy. Corticosteroids are generally not beneficial in patients with a second degree, superficial-partial thickness burn (Caravati, 2004; Howell et al, 1992).
THIRD DEGREE BURNS: Some authors have recommended steroids in this group as well (Howell et al, 1992). A high percentage of patients with third degree burns go on to develop strictures with or without corticosteroid therapy and the risk of infection and perforation may be increased by corticosteroid use. Most authors feel that the risk outweighs any potential benefit and routine use is not recommended (Boukthir et al, 2004; Oakes et al, 1982; Pelclova & Navratil, 2005).
CONTRAINDICATIONS: Include active gastrointestinal bleeding and evidence of gastric or esophageal perforation. Corticosteroids are thought to be ineffective if initiated more than 48 hours after a burn (Howell, 1987).
DOSE: Administer daily oral doses of 0.1 milligram/kilogram of dexamethasone or 1 to 2 milligrams/kilogram of prednisone. Continue therapy for a total of 3 weeks and then taper (Haller et al, 1971; Marshall, 1979). An alternative regimen in children is intravenous prednisolone 2 milligrams/kilogram/day followed by 2.5 milligrams/kilogram/day of oral prednisone for a total of 3 weeks then tapered (Anderson et al, 1990).
ANTIBIOTICS: Animal studies suggest that the addition of antibiotics can prevent the infectious complications associated with corticosteroid use in the setting of caustic burns. Antibiotics are recommended if corticosteroids are used or if perforation or infection is suspected. Agents that cover anaerobes and oral flora such as penicillin, ampicillin, or clindamycin are appropriate (Rosenberg et al, 1953).
STUDIES

ANIMAL

Some animal studies have suggested that corticosteroid therapy may reduce the incidence of stricture formation after severe alkaline corrosive injury (Haller & Bachman, 1964; Saedi et al, 1973a).
Animals treated with steroids and antibiotics appear to do better than animals treated with steroids alone (Haller & Bachman, 1964).
Other studies have shown no evidence of reduced stricture formation in steroid treated animals (Reyes et al, 1974). An increased rate of esophageal perforation related to steroid treatment has been found in animal studies (Knox et al, 1967).

HUMAN

Most human studies have been retrospective and/or uncontrolled and generally involve small numbers of patients with documented second or third degree mucosal injury. No study has proven a reduced incidence of stricture formation from steroid use in human caustic ingestions (Haller et al, 1971; Hawkins et al, 1980; Yarington & Heatly, 1963; Adam & Brick, 1982).
META ANALYSIS

Howell et al (1992), analyzed reports concerning 361 patients with corrosive esophageal injury published in the English language literature since 1956 (10 retrospective and 3 prospective studies). No patients with first degree burns developed strictures. Of 228 patients with second or third degree burns treated with corticosteroids and antibiotics, 54 (24%) developed strictures. Of 25 patients with similar burn severity treated without steroids or antibiotics, 13 (52%) developed strictures (Howell et al, 1992).
Another meta-analysis of 10 studies found that in patients with second degree esophageal burns from caustics, the overall rate of stricture formation was 14.8% in patients who received corticosteroids compared with 36% in patients who did not receive corticosteroids (LoVecchio et al, 1996).
Another study combined results of 10 papers evaluating therapy for corrosive esophageal injury in humans published between January 1991 and June 2004. There were a total of 572 patients, all patients received corticosteroids in 6 studies, in 2 studies no patients received steroids, and in 2 studies, treatment with and without corticosteroids was compared. Of 109 patients with grade 2 esophageal burns who were treated with corticosteroids, 15 (13.8%) developed strictures, compared with 2 of 32 (6.3%) patients with second degree burns who did not receive steroids (Pelclova & Navratil, 2005).

Smaller studies have questioned the value of steroids (Ferguson et al, 1989; Anderson et al, 1990), thus they should be used with caution.
Ferguson et al (1989) retrospectively compared 10 patients who did not receive antibiotics or steroids with 31 patients who received both antibiotics and steroids in a study of caustic ingestion and found no difference in the incidence of esophageal stricture between the two groups (Ferguson et al, 1989).
A randomized, controlled, prospective clinical trial involving 60 children with lye or acid induced esophageal injury did not find an effect of corticosteroids on the incidence of stricture formation (Anderson et al, 1990).

These 60 children were among 131 patients who were managed and followed-up for ingestion of caustic material from 1971 through 1988; 88% of them were between 1 and 3 years old (Anderson et al, 1990).
All patients underwent rigid esophagoscopy after being randomized to receive either no steroids or a course consisting initially of intravenous prednisolone (2 milligrams/kilogram per day) followed by 2.5 milligrams/kilogram/day of oral prednisone for a total of 3 weeks prior to tapering and discontinuation (Anderson et al, 1990).
Six (19%), 15 (48%), and 10 (32%) of those in the treatment group had first, second and third degree esophageal burns, respectively. In contrast, 13 (45%), 5 (17%), and 11 (38%) of the control group had the same levels of injury (Anderson et al, 1990).
Ten (32%) of those receiving steroids and 11 (38%) of the control group developed strictures. Four (13%) of those receiving steroids and 7 (24%) of the control group required esophageal replacement. All but 1 of the 21 children who developed strictures had severe circumferential burns on initial esophagoscopy (Anderson et al, 1990).
Because of the small numbers of patients in this study, it lacked the power to reliably detect meaningful differences in outcome between the treatment groups (Anderson et al, 1990).

ADVERSE EFFECTS

The use of corticosteroids in the treatment of caustic ingestion in humans has been associated with gastric perforation (Cleveland et al, 1963) and fatal pulmonary embolism (Aceto et al, 1970).

SEIZURES: Administer a benzodiazepine; DIAZEPAM (ADULT: 5 to 10 mg IV initially; repeat every 5 to 20 minutes as needed. CHILD: 0.1 to 0.5 mg/kg IV over 2 to 5 minutes; up to a maximum of 10 mg/dose. May repeat dose every 5 to 10 minutes as needed) or LORAZEPAM (ADULT: 2 to 4 mg IV initially; repeat every 5 to 10 minutes as needed, if seizures persist. CHILD: 0.05 to 0.1 mg/kg IV over 2 to 5 minutes, up to a maximum of 4 mg/dose; may repeat in 5 to 15 minutes as needed, if seizures continue).

Consider phenobarbital or propofol if seizures recur after diazepam 30 mg (adults) or 10 mg (children greater than 5 years).
Monitor for hypotension, dysrhythmias, respiratory depression, and need for endotracheal intubation. Evaluate for hypoglycemia, electrolyte disturbances, and hypoxia.

-RANGE OF TOXICITY

MINIMUM LETHAL EXPOSURE

ROUTE OF EXPOSURE

Fatalities have been reported following both acute and chronic exposure (HSDB , 2001; Hine, 1969).
Fatal poisoning has resulted from exposure to relatively high airborne concentrations of methyl bromide vapor (from 8,000 ppm for a few hours to 60,000 ppm for a brief exposure). Nonfatal poisoning has resulted from exposure to airborne concentrations of 35 to 500 ppm (Breeman, 2009; Bingham et al, 2001; Hathaway et al, 1996; Lewis, 1996). Another source reported exposure levels from 1600 to 60,000 ppm can result in death, depending on the duration of exposure (Breeman, 2009).

MAXIMUM TOLERATED EXPOSURE

EPA HUMAN HEALTH RISK

NON-OCCUPATIONAL (RESIDENTIAL) BYSTANDERS: An acute (1 day) inhalational exposure to methyl bromide concentrations of 0.33 ppm or higher for a 24-hour time weighted average (TWA) (Kulkarni et al, 2015).
OCCUPATIONAL HANDLERS AND BYSTANDERS: An acute (1 day) inhalational exposure to methyl bromide concentrations of 1 ppm or greater for an 8-hour time weighted average (TWA) (Kulkarni et al, 2015).

ROUTE OF EXPOSURE

INHALATION

Two men developed nausea and vomiting followed by coma, myoclonus, and seizures after workplace exposure estimated as an airborne concentration greater than 200 ppm (800 mg/m(3)) for 2 hours (Hustinx et al, 1993).
Symptoms consistent with methyl bromide and chloropicrin exposure have been reported in persons living in communities surrounding the site of field fumigation. Weather conditions in the area may have contributed to the exposures. Most common symptoms reported were non-specific and included headache and eye and throat irritation. There were also reports of shortness of breath and one child who was hallucinating. Air samples were not taken at the time of the incident. Blood bromide concentrations were not measured in any of the exposed population (Goldman et al, 1987).
Severe poisoning with some fatalities resulted from soil disinfection by injection of methyl bromide into greenhouse soil. These workers measured airborne methyl bromide levels following application rates from 30 to 3,000 ppm. They found peak values of 200 ppm existing for a few seconds upon initial injection with airborne levels above the soil declining to 4 ppm 5 days post-treatment (ACGIH, 1986).
Upon entering a building with an airborne methyl bromide concentration of 17 grams/m(3), 2 men equipped with rapidly saturable respiratory cartridges rapidly began to feel ill with nausea, dyspnea, and seizures developing in one. Long-term neurological damage was reported in the seizure victim 5 months post-exposure (Deschamps & Turpin, 1996).
CASE SERIES: Three exterminator employees developed severe methyl bromide poisoning after using 80 g/m(3) of a spray product containing 86% methyl bromide and 14% ethylene oxide to fumigate a storage room in a folklore museum. One employee left the museum after about 9 hours and developed only mild impaired consciousness. Laboratory results revealed a serum bromide concentration of 87.4 mcg/mL and urinary bromide concentration of 122.4 mcg/mg. He recovered gradually following supportive care. Patients 2 and 3 spent over 30 hours in the museum and reused the product repeatedly to increase the methyl bromide concentration to ensure adequate fumigation. Both patients developed generalized tonic-clonic seizures and impaired consciousness. Despite supportive care, including 4 dialysis sessions with direct hemoperfusion and 24-hour continuous hemodiafiltration, which reduced their serum bromide concentrations (from 164.9 mcg/mL to 6.6 mcg/mL in patient 2 and from 157.3 mcg/mL to 10.7 mcg/mL in patient 3), and long-term rehabilitation, both patients continued to have myoclonus and cognitive deficit, requiring long-term assistance. In addition, patient 3 experiences a major convulsive seizure once every several months and requires total assistance to complete activities of daily living (Yamano & Nakadate, 2006).

CASE REPORTS

A 49-year-old man developed neurological, cardiovascular, hematological, and biochemical abnormalities following exposure to methyl bromide for more than 140 hours but recovered completely following supportive treatment. The initial bromide concentration was 18 mg/100 mL (Nagaratnam et al, 1979).
Some patients who recovered from severe intoxication have had persistent central nervous system effects, including vertigo, depression, hallucinations, anxiety, and inability to concentrate (Hathaway et al, 1996).

Carcinogenicity Ratings for CAS74-83-9 :

ACGIH (American Conference of Governmental Industrial Hygienists, 2010): A4 ; Listed as: Methyl bromide

A4 :Not Classifiable as a Human Carcinogen: Agents which cause concern that they could be carcinogenic for humans but which cannot be assessed conclusively because of a lack of data. In vitro or animal studies do not provide indications of carcinogenicity which are sufficient to classify the agent into one of the other categories.

EPA (U.S. Environmental Protection Agency, 2011): D ; Listed as: Bromomethane

D : Not classifiable as to human carcinogenicity.

IARC (International Agency for Research on Cancer (IARC), 2016; International Agency for Research on Cancer, 2015; IARC Working Group on the Evaluation of Carcinogenic Risks to Humans, 2010; IARC Working Group on the Evaluation of Carcinogenic Risks to Humans, 2010a; IARC Working Group on the Evaluation of Carcinogenic Risks to Humans, 2008; IARC Working Group on the Evaluation of Carcinogenic Risks to Humans, 2007; IARC Working Group on the Evaluation of Carcinogenic Risks to Humans, 2006; IARC, 2004): 3 ; Listed as: Methyl bromide

3 : The agent (mixture or exposure circumstance) is not classifiable as to its carcinogenicity to humans. This category is used most commonly for agents, mixtures and exposure circumstances for which the evidence of carcinogenicity is inadequate in humans and inadequate or limited in experimental animals. Exceptionally, agents (mixtures) for which the evidence of carcinogenicity is inadequate in humans but sufficient in experimental animals may be placed in this category when there is strong evidence that the mechanism of carcinogenicity in experimental animals does not operate in humans. Agents, mixtures and exposure circumstances that do not fall into any other group are also placed in this category.

NIOSH (National Institute for Occupational Safety and Health, 2007): Ca ; Listed as: Methyl bromide

Ca : NIOSH considers this substance to be a potential occupational carcinogen (See Appendix A in the NIOSH Pocket Guide to Chemical Hazards).

MAK (DFG, 2002): Category 3B ; Listed as: Methyl bromide

Category 3B : Substances for which in vitro or animal studies have yielded evidence of carcinogenic effects that is not sufficient for classification of the substance in one of the other categories. Further studies are required before a final decision can be made. A MAK value can be established provided no genotoxic effects have been detected. (Footnote: In the past, when a substance was classified as Category 3 it was given a MAK value provided that it had no detectable genotoxic effects. When all such substances have been examined for whether or not they may be classified in Category 4, this sentence may be omitted.)

NTP (U.S. Department of Health and Human Services, Public Health Service, National Toxicology Project ): Not Listed

TOXICITY AND RISK ASSESSMENT VALUES

EPA IRIS

EPA Risk Assessment Values for CAS74-83-9 (U.S. Environmental Protection Agency, 2011):

Oral:

Slope Factor:
RfD: 1.4x10(-3) mg/kg-day

Inhalation:

Unit Risk:
RfC: 5x10(-3) mg/m3

Drinking Water:

Unit Risk:

TOXICITY VALUES

References: ACGIH, 1991 EPA, 1986; HSDB, 2001 ITI, 1995 Lewis, 1996 OHM/TADS, 1999 RTECS, 2001
- LC- (INHALATION)GUINEA_PIG:
- LC- (INHALATION)RABBIT:
- LC- (INHALATION)RAT:
- LC50- (INHALATION)MOUSE:
- LC50- (INHALATION)RABBIT:
- LC50- (INHALATION)RAT:
- LCLo- (INHALATION)GUINEA_PIG:
- LCLo- (INHALATION)HUMAN:
- LCLo- (INHALATION)HUMAN:
- LCLo- (INHALATION)RABBIT:
- LCLo- (INHALATION)RAT:
- LD50- (INHALATION)RAT:
- LD50- (ORAL)RAT:
- LD50- (SUBCUTANEOUS)RAT:
- LDLo- (ORAL)DOG:
- TCLo- (INHALATION)HUMAN:
- TCLo- (INHALATION)HUMAN:
- TDLo- (SKIN)HUMAN:
- TDLo- (ORAL)RABBIT:
- TDLo- (ORAL)RAT:

CALCULATIONS

AMBIENT CONVERSIONS

CONVERSION FACTOR

1 ppm = 3.89 mg/m(3) (at 68 degrees F and 760 mmHg) (NIOSH , 1999)

-STANDARDS AND LABELS

WORKPLACE STANDARDS

ACGIH TLV Values for CAS74-83-9 (American Conference of Governmental Industrial Hygienists, 2010):

Editor's Note: The listed values are recommendations or guidelines developed by ACGIH(R) to assist in the control of health hazards. They should only be used, interpreted and applied by individuals trained in industrial hygiene. Before applying these values, it is imperative to read the introduction to each section in the current TLVs(R) and BEI(R) Book and become familiar with the constraints and limitations to their use. Always consult the Documentation of the TLVs(R) and BEIs(R) before applying these recommendations and guidelines.

Adopted Value

Methyl bromide

TLV:

TLV-TWA: 1 ppm
TLV-STEL:
TLV-Ceiling:

Notations and Endnotes:

Carcinogenicity Category: A4
Codes: Skin
Definitions:

A4: Not Classifiable as a Human Carcinogen: Agents which cause concern that they could be carcinogenic for humans but which cannot be assessed conclusively because of a lack of data. In vitro or animal studies do not provide indications of carcinogenicity which are sufficient to classify the agent into one of the other categories.
Skin: This refers to the potential significant contribution to the overall exposure by the cutaneous route, including mucous membranes and the eyes, either by contact with vapors or, of likely greater significance, by direct skin contact with the substance. It should be noted that although some materials are capable of causing irritation, dermatitis, and sensitization in workers, these properties are not considered relevant when assigning a skin notation. Rather, data from acute dermal studies and repeated dose dermal studies in animals or humans, along with the ability of the chemical to be absorbed, are integrated in the decision-making toward assignment of the skin designation. Use of the skin designation provides an alert that air sampling would not be sufficient by itself in quantifying exposure from the substance and that measures to prevent significant cutaneous absorption may be warranted. Please see "Definitions and Notations" (in TLV booklet) for full definition.

TLV Basis - Critical Effect(s): URT and skin irr
Molecular Weight: 94.95

For gases and vapors, to convert the TLV from ppm to mg/m(3):

[(TLV in ppm)(gram molecular weight of substance)]/24.45

For gases and vapors, to convert the TLV from mg/m(3) to ppm:

[(TLV in mg/m(3))(24.45)]/gram molecular weight of substance

AIHA WEEL Values for CAS74-83-9 (AIHA, 2006):

Not Listed

NIOSH REL and IDLH Values for CAS74-83-9 (National Institute for Occupational Safety and Health, 2007):

Listed as: Methyl bromide
REL:

TWA:
STEL:
Ceiling:
Carcinogen Listing: (Ca) NIOSH considers this substance to be a potential occupational carcinogen (See Appendix A in the NIOSH Pocket Guide to Chemical Hazards).
Skin Designation: Not Listed
Note(s): See Appendix A

IDLH:

IDLH: 250 ppm
Note(s): Ca

Ca: NIOSH considers this substance to be a potential occupational carcinogen (See Appendix A).

OSHA PEL Values for CAS74-83-9 (U.S. Occupational Safety, and Health Administration (OSHA), 2010):

Listed as: Methyl bromide
Table Z-1 for Methyl bromide:

8-hour TWA:

ppm: 20

Parts of vapor or gas per million parts of contaminated air by volume at 25 degrees C and 760 torr.

mg/m3: 80

Milligrams of substances per cubic meter of air. When entry is in this column only, the value is exact; when listed with a ppm entry, it is approximate.

Ceiling Value: (C) - An employee's exposure to this substance shall at no time exceed the exposure limit given.
Skin Designation: Yes
Notation(s): Not Listed

OSHA List of Highly Hazardous Chemicals, Toxics, and Reactives for CAS74-83-9 (U.S. Occupational Safety and Health Administration, 2010):

Threshold Quantity, in pounds:2500

ENVIRONMENTAL STANDARDS

EPA CERCLA, Hazardous Substances and Reportable Quantities for CAS74-83-9 (U.S. Environmental Protection Agency, 2010):

Listed as: Bromomethane
Final Reportable Quantity, in pounds (kilograms):

1000 (454)

Additional Information:
Listed as: Methane, bromo-
Final Reportable Quantity, in pounds (kilograms):

1000 (454)

Additional Information:
Listed as: Methyl bromide
Final Reportable Quantity, in pounds (kilograms):

1000 (454)

Additional Information:

EPA CERCLA, Hazardous Substances and Reportable Quantities, Radionuclides for CAS74-83-9 (U.S. Environmental Protection Agency, 2010):

Not Listed

EPA RCRA Hazardous Waste Number for CAS74-83-9 (U.S. Environmental Protection Agency, 2010b):

Listed as: Methane, bromo-
P or U series number: U029
Footnote:
Listed as: Methyl bromide
P or U series number: U029
Footnote:
Editor's Note: The D, F, and K series waste numbers and Appendix VIII to Part 261 -- Hazardous Constituents were not included. Please refer to 40 CFR Part 261.

EPA SARA Title III, Extremely Hazardous Substance List for CAS74-83-9 (U.S. Environmental Protection Agency, 2010):

Listed as: Methyl Bromide
Reportable Quantity, in pounds: 1000

Only the statutory or final RQ is shown. For more information, see 40 CFR table 302.4.

Threshold Planning Quantity, in pounds:

1000
Amount necessary to be covered by this standard. See 40 CFR 355.30.

Note(s): f

f: Chemicals on the original list that do not meet toxicity criteria but because of their acute lethality, high production volume and known risk are considered chemicals of concern ("Other chemicals"). (November 17, 1986, and February 15, 1990.)

EPA SARA Title III, Community Right-to-Know for CAS74-83-9 (40 CFR 372.65, 2006; 40 CFR 372.28, 2006):

Listed as: Bromomethane (Methyl bromide)
Effective Date for Reporting Under 40 CFR 372.30: 1/1/87
Lower Thresholds for Chemicals of Special Concern under 40 CFR 372.28:

DOT List of Marine Pollutants for CAS74-83-9 (49 CFR 172.101 - App. B, 2005):

Listed as Methyl bromide and ethylene dibromide mixtures, liquid
Severe Marine Pollutant: No
Listed as Ethylene dibromide and methyl bromide mixtures, liquid
Severe Marine Pollutant: No

EPA TSCA Inventory for CAS74-83-9 (EPA, 2005):

Listed as: Methane, bromo-

SHIPPING REGULATIONS

SURFACE

DOT -- Table of Hazardous Materials and Special Provisions for UN/NA Number 1062 (49 CFR 172.101, 2005):

Hazardous materials descriptions and proper shipping name: Methyl bromide

Symbol(s): Not Listed
Hazard class or Division: 2.3

2.3: Poisonous gas. See 49 CFR section 173.115 for definitions.

Identification Number: UN1062
Packing Group: Not Listed
Label(s) required (if not excepted): 2.3

2.3: Poison Gas.

Special Provisions: 3, B14, T50

3: This material is poisonous by inhalation (see sxn. 171.8 of this subchapter) in Hazard Zone C (see sxn. 173.116(a) of this subchapter), and must be described as an inhalation hazard under the provisions of this subchapter.
B14: Each bulk packaging, except a tank car or a multi-unit-tank car tank, must be insulated with an insulating material so that the overall thermal conductance at 15.5 °C (60 °F) is no more than 1.5333 kilojoules per hour per square meter per degree Celsius (0.075 Btu per hour per square foot per degree Fahrenheit) temperature differential. Insulating materials must not promote corrosion to steel when wet.
T50: Applicable liquefied compressed gases are authorized to be transported in portable tanks in accordance with the requirements of sxn. 173.313 of this subchapter.

Packaging Authorizations (refer to 49 CFR 173.***):

Exceptions: None
Non-bulk packaging: 193
Bulk packaging: 314, 315

Quantity Limitations:

Passenger aircraft or railcar: Forbidden
Cargo aircraft only: Forbidden

Vessel Stowage Requirements:

Vessel stowage location: D

D: The material must be stowed "on deck only" on a cargo vessel and on a passenger vessel carrying a number of passengers limited to not more than the larger of 25 passengers or one passenger per each 3 m of overall vessel length, but the material is prohibited on passenger vessels in which the limiting number of passengers is exceeded.

Vessel stowage other: 40

40: Stow "clear of living quarters".

ICAO International Shipping Name for UN1062 (ICAO, 2002):

Proper Shipping Name: Methyl bromide with not more than 2% chloropicrin
UN Number: 1062

LABELS

NFPA

NFPA Hazard Ratings for CAS74-83-9 (NFPA, 2002):

Listed as: Methyl Bromide
Hazard Ratings:

Health Rating (Blue): 3

(3) Seriously toxic material. Short term exposure could cause serious temporary or residual injury even though prompt medical treatment is given. Includes known or suspect small animal carcinogens, mutagens, or teratogens.

Flammability Rating (Red): 1

(1) Slightly combustible. Materials that require considerable preheating before ignition can occur. This rating includes most ordinary combustible materials.

Instability Rating (Yellow): 0

(0) Materials which are normally stable, even under fire conditions, and which are not reactive with water.

Oxidizer/Water-Reactive Designation: Not Listed

-HANDLING AND STORAGE

HANDLING

Persons should not handle broken packages of methyl bromide unless wearing appropriate protective clothing (AAR, 1996).

STORAGE

CONTAINER

Usual shipping containers include cans, steel cylinders, and tank cars (NFPA, 1997). Containers should be stored in a well-ventilated, cool place away from direct sunlight. Room temperature should be below 40 degrees C and all heat sources should be avoided. Containers should be protected from physical damage (Sittig, 1991). Only specified equipment should be used when opening or sealing containers of methyl bromide (CHRIS , 1999).
Methyl bromide is not corrosive to metal containers, but traces of water or acid may lead to the corrosion of application equipment (EPA, 1988). Methyl bromide will hydrolyze very slowly in water, and more rapidly in an alkaline media (HSDB , 1999).

ROOM/CABINET RECOMMENDATIONS

Methyl bromide is a liquid below 38 degrees F and is shipped as a liquified, compressed gas (NIOSH , 1999).
The temperature should be lower than 40 degrees C (HSDB , 1999).
Methyl bromide should be stored in a cool, dry, well-ventilated location and kept isolated from active metals (NFPA, 1997). Vents should have calcium chloride traps (CHRIS , 1999).
Cylinders should be stored outside or in a detached storage area out of direct sunlight and protected from snow and ice (NFPA, 1997). Containers should be protected from physical damage. One-pound containers should be stored in a dry location to prevent rusting (HSDB , 1999). Contents are under pressure and should be opened with care (CGA, 1990).
Cylinders should be stored in upright, secured racks or walls to prevent tipping. Containers should not be handled roughly or subjected to mechanical shock (dropping, bumping, dragging, or sliding). Safety caps and valve protection bonnets should be replaced when cylinders are not in use. Empty cylinders should have the valves closed, safety caps screwed on to the valve outlet, and protection bonnets replaced before returning them to the shipper (HSDB , 1999).

INCOMPATIBILITIES

Methyl bromide forms an explosive compound on contact with aluminum (ITI, 1995). Keep this compound away from strong oxidizers (Sittig, 1991).

-PERSONAL PROTECTION

SUMMARY

RECOMMENDED PROTECTIVE CLOTHING - EMERGENCY RESPONSE GUIDEBOOK, GUIDE 123 (ERG, 2004)

Wear positive pressure self-contained breathing apparatus (SCBA).
Wear chemical protective clothing that is specifically recommended by the manufacturer. It may provide little or no thermal protection.
Structural firefighters' protective clothing provides limited protection in fire situations ONLY; it is not effective in spill situations where direct contact with the substance is possible.

Persons applying methyl bromide should wear loose, cotton, long-sleeved shirts and pants, shoes, and socks. Clothing should be cleaned after each use. Boots and gloves should not be worn while working with methyl bromide because the compound is heavier than air and may become trapped inside clothing and skin injury could occur (EPA, 1988). Persons should not wear leather or rubber clothing because these materials may absorb methyl bromide and cause skin contact (OHM/TADS , 1999).

All contaminated clothing should be removed and washed promptly. Affected skin should be washed immediately with copious amounts of soap and water (AAR, 1996). Skin should then be washed with a 2% aqueous solution of sodium bicarbonate (HSDB , 1999). Persons should wear appropriate protective equipment to prevent skin and eye contact. Emergency showers should be provided (Sittig, 1991).

Industrial operations that regularly use methyl bromide should have some kind of warning or monitoring system for continuous analysis of air (Clayton & Clayton, 1994).

Fumigation operations should also have suitable analytical equipment and personnel must have proper protective equipment (Clayton & Clayton, 1994). Equipment should not include aluminum or magnesium parts (or their alloys) (OHM/TADS , 1999). Because this compound can readily penetrate the skin, gas masks are relatively ineffective (HSDB , 1999).

Methyl bromide should only be used by persons who are well-acquainted with proper handling methods and are fully aware of the consequences of excessive exposure (HSDB , 1999).

EYE/FACE PROTECTION

Contact lenses should not be worn when working with methyl bromide (HSDB , 1999).

RESPIRATORY PROTECTION

Refer to "Recommendations for respirator selection" in the NIOSH Pocket Guide to Chemical Hazards on TOMES Plus(R) for respirator information.

PROTECTIVE CLOTHING

CHEMICAL PROTECTIVE CLOTHING. Search results for CAS 74-83-9.

All data are compiled from published sources and are NOT recommended specifically by Truven Health Analytics. The appearance of specific manufacturers or products in this section does not represent an endorsement by Truven Health Analytics. No attempt has been made to verify the data presented. All product recommendations should be confirmed with the specific manufacturer for verification of product performance.
CLOTHING

Neoprene

River City

Neoprene splash suits

Degradation Rating: Good
Breakthrough Time (minutes): Not Listed
Permeation Rate (mcg/cm2/min): Not Listed
Notes: Not Listed
Citation: (River City, 1995)

Plastic Laminate

DuPont Personal Protection

Responder

Degradation Rating: No Degradation Rating provided
Breakthrough Time (minutes): >480
Permeation Rate (mcg/cm2/min): None detected
Notes: Not Listed
Citation: (DuPont, 2002)

Responder Plus

Degradation Rating: No Degradation Rating provided
Breakthrough Time (minutes): >480
Permeation Rate (mcg/cm2/min): None detected
Notes: Not Listed
Citation: (DuPont, 2002)

Tychem 10,000

Degradation Rating: No Degradation Rating provided
Breakthrough Time (minutes): >480
Permeation Rate (mcg/cm2/min): 0.03
Notes: gas
Citation: (DuPont, 2002)

Tychem 7500

Degradation Rating: No Degradation Rating provided
Breakthrough Time (minutes): Not Tested
Permeation Rate (mcg/cm2/min): Not Tested
Notes: gas
Citation: (DuPont, 2002)

Tychem 9400

Degradation Rating: No Degradation Rating provided
Breakthrough Time (minutes): >480
Permeation Rate (mcg/cm2/min): <0.01
Notes: gas
Citation: (DuPont, 2002)

Tychem BR

Degradation Rating: No Degradation Rating provided
Breakthrough Time (minutes): >480
Permeation Rate (mcg/cm2/min): <0.01
Notes: Not Listed
Citation: (DuPont, 2002)

Tychem LV

Degradation Rating: Not Listed
Breakthrough Time (minutes): >480
Permeation Rate (mcg/cm2/min): <0.01
Notes: Not Listed
Citation: (DuPont, 2003)

Tychem QC

Degradation Rating: No Degradation Rating provided
Breakthrough Time (minutes): Not Tested
Permeation Rate (mcg/cm2/min): Not Tested
Notes: gas
Citation: (DuPont, 2002)

Tychem SL

Degradation Rating: No Degradation Rating provided
Breakthrough Time (minutes): >480
Permeation Rate (mcg/cm2/min): <0.01
Notes: Not Listed
Citation: (DuPont, 2002)
Degradation Rating: No Degradation Rating provided
Breakthrough Time (minutes): >480
Permeation Rate (mcg/cm2/min): <0.1
Notes: gas
Citation: (DuPont, 2002)

Tychem TK

Degradation Rating: No Degradation Rating provided
Breakthrough Time (minutes): >480
Permeation Rate (mcg/cm2/min): <0.01
Notes: Not Listed
Citation: (DuPont, 2002)
Degradation Rating: No Degradation Rating provided
Breakthrough Time (minutes): >480
Permeation Rate (mcg/cm2/min): <0.01
Notes: gas
Citation: (DuPont, 2002)

Polyvinyl Chloride

River City

PVC splash suits

Degradation Rating: Not Recommended
Breakthrough Time (minutes): Not Listed
Permeation Rate (mcg/cm2/min): Not Listed
Notes: Not Listed
Citation: (River City, 1995)

Teflon Laminate

Mar-Mac Manufacturing, Inc.

Commander Ultrapro

Degradation Rating: No Degradation Rating provided
Breakthrough Time (minutes): >480
Permeation Rate (mcg/cm2/min): <0.1
Notes: Not Listed
Citation: (Mar-Mac Manufacturing, Inc, 1995)

FOOTWEAR

Specific recommendations and test data for this product type were not found in the available manufacturers' product literature.

GLOVES

Natural Rubber

Boss Manufacturing Company

Not specified

Degradation Rating: Fair
Breakthrough Time (minutes): Not Listed
Permeation Rate (mcg/cm2/min): Not Listed
Notes: Not Listed
Citation: (Boss Manufacturing Company, 1998)

Neoprene

Boss Manufacturing Company

Not specified

Degradation Rating: Not Recommended
Breakthrough Time (minutes): Not Listed
Permeation Rate (mcg/cm2/min): Not Listed
Notes: Not Listed
Citation: (Boss Manufacturing Company, 1998)

Nitrile

Boss Manufacturing Company

Not specified

Degradation Rating: Good
Breakthrough Time (minutes): Not Listed
Permeation Rate (mcg/cm2/min): Not Listed
Notes: Not Listed
Citation: (Boss Manufacturing Company, 1998)

Polyvinyl Chloride

Boss Manufacturing Company

Not specified

Degradation Rating: Poor
Breakthrough Time (minutes): Not Listed
Permeation Rate (mcg/cm2/min): Not Listed
Notes: Not Listed
Citation: (Boss Manufacturing Company, 1998)

GENERAL INFORMATION

This section provides a compilation of chemical resistance information and test data for specific protective clothing products. Chemical resistance information includes both degradation resistance ratings and permeation resistance data. This information is designed to assist in the selection of appropriate protective clothing. Only data on specific products and manufacturers are included. Generic information or recommendations are not provided since significant differences can exist in the chemical resistance for apparent similar product types.
Specific product information is organized by general product type (gloves, garments, and footwear), material type, and manufacturer. The category 'garments' may include totally encapsulating suits, splash suits, as well as other items (e.g., coveralls, jackets, and aprons). Specific manufacturers should be contacted to determine the features of available styles/models.
In addition to chemical resistance information, there are many critical variables in the selection of protective clothing which cannot be represented in this summary of the literature. Some factors to be considered in choosing protective clothing include, but are not limited to: overall clothing integrity, physical hazard resistance, durability, human factors, ease of decontamination, and cost. Overall clothing integrity refers to a specific design's ability to offer consistent protection for all clothing-covered areas of the body. Physical hazards include resisting the effects of abrasion, cuts, tears, and punctures. Human factors entail effects on wearer mobility, visibility, and hearing for garments; dexterity, tactility, and grip for gloves; ankle support and weight for footwear; and, any effect of the clothing on the function of the wearer. There are several variations in the design for gloves, garments, and footwear that affect these factors. Protective clothing must properly be sized and correctly fit the wearer to ensure its proper use and function.
As required in the U.S.A., protective clothing should be selected based on a risk assessment of the workplace. This risk assessment must account for the identification of existing as well as potential hazards and involve the recommendation of protective clothing appropriate for the identified hazards. Therefore, the recommendations in this section should not be used as the sole basis for decisions on choice of protective clothing, but rather should be used as a tool by qualified occupational health and safety professionals or other technically qualified persons in conjunction with a review of all mitigating factors. Consult the OSHA PPE Standard (29 CFR 1910.132 - 1910.138) for regulations and additional guidance regarding the selection and use of protective clothing and equipment. For general information on protective clothing selection, refer to the "PERSONAL PROTECTIVE EQUIPMENT - OSHA PUB 3077" document.
PROTECTIVE CLOTHING SELECTION

Determine the type of protective clothing item needed based on a risk assessment (e.g., gloves, garments, footwear).
For high risk situations, choose clothing that covers all parts of the body that may be exposed. In many cases, multiple clothing items will be required. Low risk situations may permit partial body protective clothing. Select protective clothing products that have reported chemical resistance data. High risk situations involving full body clothing or extended chemical contact often require permeation resistance data to determine the barrier effectiveness of materials used in the construction of clothing. Relatively low risk situations, where only splash or incidental exposure occur, may allow use of protective clothing based on degradation or penetration resistance data. Specifics on the interpretation of chemical resistance data are presented below.
Other factors must be considered in addition to chemical resistance. The selected chemical protective clothing item should offer the optimal combination of protection against identified hazards while allowing maximum function and comfort.

INTERPRETATION OF DEGRADATION RATINGS

Degradation refers to physical changes in a material as the result of chemical exposure. Degradation may become evident in visible changes, such as discoloration, swelling, delamination, deterioration, or disintegration. Degradation effects may also be measured by weight change or other changes in a material's physical properties (e.g., strength, elasticity, hardness).
Degradation resistance ratings are provided by manufacturers to rate the amount of degradation that occurs for a particular protective clothing material when contacted by a chemical. All degradation ratings are qualitative and include ratings, such as "EXCELLENT," "GOOD," "FAIR," "POOR," and "NOT RECOMMENDED." There is no standard test method for the measurement of chemical degradation resistance; therefore, manufacturer ratings may be based on different testing approaches. This makes comparison of degradation ratings between manufacturers unreliable.
The use of degradation resistance ratings alone to recommend protective clothing, particularly for high hazard situations, should be avoided. Degradation resistance testing does not directly assess the barrier quality of protective clothing, since materials can show relatively little degradation but still allow either permeation or penetration by a chemical. Degradation resistance ratings can be used to exclude protective clothing materials from consideration. Protective clothing materials with a "NOT RECOMMENDED" degradation resistance rating should never be used.
For some products, the rating "NO PENETRATION" is provided. This refers to penetration resistance test results that are based on a different procedure (American Society for Testing and Materials (ASTM) Standard Test Method F 903). Penetration resistance testing involves placing a material sample in a test cell, exposing the exterior side of the material to a chemical, and then observing the interior side of the material for visible signs of liquid penetration. Part of the test is conducted at an elevated pressure. Test results are reported as pass (no penetration) or fail (penetration detected). Unlike degradation testing, penetration testing provides an assessment of protective clothing material barrier performance. Since penetration resistance testing examines only observable amounts of liquid penetration, permeation may still occur. The use of penetration resistance data must be restricted to liquid chemicals, and should be limited to scenarios where there is no reasonable vapor exposure hazard under the conditions of exposure.

INTERPRETATION OF PERMEATION DATA

Permeation is the process of chemical movement through a material on a molecular level. Permeation resistance refers to the ability of a material to retard or prevent chemical movement through it. Permeation may occur without any visible signs of degradation.
Permeation resistance is measured using a test cell which is divided into two halves by a protective clothing specimen. Chemical is placed on the challenge side, while the collection side is periodically monitored for permeating chemical. Permeation data were obtained in accordance with the American Society for Testing and Materials (ASTM) Standard Test Method F 739 (Resistance of Materials Used in Protective Clothing to Permeation by Liquids and Gases), unless stated otherwise. In the case of chemicals that are classified as warfare agents, the data were obtained in accordance with the Military Standard 282 (MIL-STD-282) (Military Standard, Filter Units, Protective Clothing, Gas-Mask Components, and Related Products: Performance Test Methods).
Permeation rate is the amount of chemical that passes through a material for a measured surface area per unit time. In this section, permeation rate is expressed in micrograms per square centimeter per minute (mcg/cm(2)/min). The reported permeation rate is either the steady-state rate or the maximum rate observed during testing. In some cases, very large permeation rates exceed measurement techniques and are reported as ">" (greater than) or "HIGH."
Breakthrough time is the elapsed time, in minutes, from the time the chemical comes in contact with the material exterior surface, to the time that chemical is detected on the interior surface. When no breakthrough is detected, the breakthrough time is report as ">" the testing period. If permeation breakthrough is rapid, results are reported as "<" (less than) the earlier sampling time or as "IMMEDIATELY" (which usually means breakthrough in less than 4 minutes).
The breakthrough time should exceed the expected use period of the selected protective clothing. Additionally, there are several other factors that must be taken into account to provide appropriate protection.
Permeation testing is usually conducted with full strength, undiluted chemical for the duration of the test period. Actual exposures may involve diluted chemical for short or intermittent exposure periods.
Permeation testing is usually conducted at room temperature. Permeation occurs faster at elevated temperatures (short breakthrough times and higher permeation rates) and slower at reduced temperatures (long breakthrough times and lower permeation rates).
Permeation resistance of mixtures cannot usually be determined on the basis of the individual chemicals making up the mixture. Synergistic effects may occur and result in more rapid permeation than accounted for by the individual mixture chemicals.
Permeation rates may be used to calculate potential wearer exposure; however, several assumptions must be made about the extent of exposure and condition of clothing wear. Furthermore, there are few chemicals with dermal exposure limits, making it difficult to determine an acceptable skin exposure level.

COMPANY INFORMATION

Boss Manufacturing Company 221 W. First Street Kewanee, IL 61443 USA Phone: (309) 852-2131 Fax: (309) 852-0848 Toll-Free: (800) 447-4581 Website: http://www.bossgloves.com Email: custserv@bossgloves.com
DuPont Personal Protection P. O. Box 80705 Wilmington, DE 19880-0705 USA Phone: (302) 774-1000 Toll-Free: (800) 931-3456 Website: http://personalprotection.dupont.com Email: personalprotection@usa.dupont.com
Mar-Mac Manufacturing, Inc. P. O. Box P.O. Box 278 McBee, SC 29101 USA Phone: (843) 335-8211 Fax: (843) 355-8599 Toll-Free: (843) 335-8211 Website: http://www.marmac.com Email: info@marmac.com
River City 5321 East Shelby Dr. Memphis, TN 38188 USA Phone: (800) 888-0347 Fax: (901) 795-3815 Toll-Free: (800) 888-0347 Website: http://www.protectivewear.com Email: support@protectivewear.com

REFERENCES

CHEMICAL PROTECTIVE CLOTHING CITATIONS

The following sources were consulted for chemical protective clothing data:

(Ansell-Edmont, 2001)
(Bata Shoe Company, 1995)
(Best Manufacturing, 2002)
(Best Manufacturing, 2004)
(Boss Manufacturing Company, 1998)
(ChemFab Corporation, 1993)
(Comasec Safety, Inc., 2003)
(Comasec Safety, Inc., 2003a)
(DuPont, 2002)
(DuPont, 2002)
(DuPont, 2003)
(Guardian Manufacturing Group, 2001)
(ILC Dover, Inc., 1998)
(Kappler Inc., 2001)
(Kimberly-Clark, 2002)
(LaCrosse-Rainfair, 1997)
(MAPA Professional, 2003)
(MAPA Professional, 2004)
(Mar-Mac Manufacturing, Inc, 1995)
(Marigold Industrial, 2003)
(Memphis Glove Company, 2001)
(Montgomery Safety Products, 1995)
(Nat-Wear, 2001)
(Neese Industries, Inc., 2003)
(North, 2002)
(North, 2002)
(Playtex, 1995)
(River City, 1995)
(Safety 4, 2002)
(Servus, 1995)
(Standard Safety Equipment, 1995)
(Tingley, 2002)
(Trelleborg-Viking, Inc., 2001)
(Trelleborg-Viking, Inc., 2002)
(Wells Lamont Industrial, 2002)
(Workrite, 1997)

-PHYSICAL HAZARDS

FIRE HAZARD

SUMMARY

POTENTIAL FIRE OR EXPLOSION HAZARDS - EMERGENCY RESPONSE GUIDEBOOK, GUIDE 123 (ERG, 2004)
- Some may burn, but none ignite readily.
- Vapors from liquefied gas are initially heavier than air and spread along ground.
- Cylinders exposed to fire may vent and release toxic and/or corrosive gas through pressure relief devices.
- Containers may explode when heated.
- Ruptured cylinders may rocket.
Methyl bromide is not ordinarily considered to be combustible; however, it will burn in air in the presence of a high heat source (within a narrow flammability range) and strong oxidizers (Lewis, 1996; NFPA, 1997). It will burn at 536 degrees C (Sittig, 1991). Methyl bromide is moderately explosive when exposed to flame or sparks (Lewis, 1996).
Ten to fifteen percent mixtures with air may be ignited with difficulty (Lewis, 1996).
This compound is non-flammable in air, but burns in oxygen (Budavari, 1996).
Methyl bromide will attack aluminum and form aluminum trimethyl, which is spontaneously flammable (NIOSH , 1999).

FLAMMABILITY CLASSIFICATION

NFPA Flammability Rating for CAS74-83-9 (NFPA, 2002):

Listed as: Methyl Bromide
Flammability Rating: 1

(1) Slightly combustible. Materials that require considerable preheating before ignition can occur. This rating includes most ordinary combustible materials.

FIRE CONTROL/EXTINGUISHING AGENTS

SMALL FIRE PRECAUTIONS - EMERGENCY RESPONSE GUIDEBOOK, GUIDE 123 (ERG, 2004)

Dry chemical or CO2.

LARGE FIRE PRECAUTIONS - EMERGENCY RESPONSE GUIDEBOOK, GUIDE 123 (ERG, 2004)

Water spray, fog or regular foam.
Do not get water inside containers.
Move containers from fire area if you can do it without risk.
Damaged cylinders should be handled only by specialists.

TANK FIRE PRECAUTIONS - EMERGENCY RESPONSE GUIDEBOOK, GUIDE 123 (ERG, 2004)

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

NFPA Extinguishing Methods for CAS74-83-9 (NFPA, 2002):

Listed as: Methyl Bromide
Extinguishing Method(s): Not Listed

Fires should be approached from upwind to avoid hazardous vapors and toxic decomposition products (NFPA, 1997). Hydrogen bromide and carbon monoxide may be released during a fire involving methyl bromide (HSDB , 1999).

Fires involving methyl bromide should be extinguished using an agent suitable for type of surrounding fire (material itself does not burn or burns with difficulty). Water, in flooding quantities, may be used as a fog. Affected containers may be cooled with flooding quantities of water. Apply water from as far a distance as possible. Use foam, dry chemical, or carbon dioxide (AAR, 1996; (Lewis, 1996; NFPA, 1997; Sittig, 1991).

COMBUSTION TOXICITY

Thermal decomposition (from contact with hot surface or open flame) include hydrogen bromide, bromine, and carbon oxybromide, carbon dioxide, and carbon monoxide. Hydrogen bromide and carbon monoxide may be released during a fire involving methyl bromide (HSDB , 1999).

EXPLOSION HAZARD

When exposed to sparks or flame, methyl bromide is moderately explosive (Lewis, 1996).

This compound can form explosive mixtures with air within narrow limits at atmospheric pressure, with wider limits at higher pressure. Explosion sensitivity of mixtures with air may be increased in the presence of aluminum; magnesium; zinc; or their alloys (Lewis, 1996).

A reaction between methyl bromide and dimethyl sulfoxide (when heated to 65 degrees C), resulted in an explosion (after 120 hours) that shattered the testing apparatus (NFPA, 1997; Urben, 1996).

DUST/VAPOR HAZARD

Thermal decomposition products (from contact with a hot surface or open flame) include hydrogen bromide, bromine, and carbon oxybromide, carbon dioxide, and carbon monoxide (HSDB , 1999).

When heated to decomposition, this compound emits toxic fumes of hydrogen bromide (Lewis, 1996).

REACTIVITY HAZARD

Methyl bromide is incompatible with metals; dimethyl sulfoxide; and ethylene oxide (Lewis, 1996).

Methyl bromide will attack aluminum to form aluminum trimethyl, which is spontaneously flammable (NIOSH , 1999).

Methyl bromide is incompatible with aluminum or strong oxidizers (Sittig, 1991).

In the presence of moisture, methyl bromide is corrosive to tin, magnesium, zinc, and other alloys (HSDB , 1999).

Metallic components of zinc, aluminum, and magnesium (or their alloys) are unsuitable with bromomethane because of the formation of pyrophoric Grignard-type compounds (Urben, 1996). "A severe explosion is attributed to ignition of a bromomethane-air mixture by pyrophoric methylaluminum bromides produced by corrosion of an aluminum component" (HSDB , 1999).

EVACUATION PROCEDURES

SUMMARY

Initial Isolation and Protective Action Distances (ERG, 2004)

Data presented from the Emergency Response Guidebook Table of Initial Isolation and Protective Action Distances are for use when a spill has occurred and there is no fire. If there is a fire, or if a fire is involved, evacuation information presented under FIRE - PUBLIC SAFETY EVACUATION DISTANCES should be used.
Generally, a small spill is one that involves a single, small package such as a drum containing up to approximately 200 liters, a small cylinder, or a small leak from a large package. A large spill is one that involves a spill from a large package, or multiple spills from many small packages.
Suggested distances to protect from vapors of toxic-by-inhalation and/or water-reactive materials during the first 30 minutes following the spill.

DOT ID No. 1062 - Methyl bromide

SMALL SPILLS

First isolate in all directions: 30 meters (100 feet).
Note wind direction.
Then protect persons downwind:

during the DAY for: 0.1 kilometers (0.1 miles); or
during the NIGHT for: 0.2 kilometers (0.1 miles).

LARGE SPILLS

First isolate in all directions: 90 meters (300 feet).
Note wind direction.
Then protect persons downwind:

during the DAY for: 0.7 kilometers (0.5 miles); or
during the NIGHT for: 2.2 kilometers (1.4 miles).

SPILL - PUBLIC SAFETY EVACUATION DISTANCES - EMERGENCY RESPONSE GUIDEBOOK, GUIDE 123 (ERG, 2004)

Increase, in the downwind direction, as necessary, the isolation distance of at least 100 meters (330 feet) in all directions.

FIRE - PUBLIC SAFETY EVACUATION DISTANCES - EMERGENCY RESPONSE GUIDEBOOK, GUIDE 123 (ERG, 2004)

If tank, rail car or tank truck is involved in a fire, ISOLATE for 800 meters (1/2 mile) in all directions; also, consider initial evacuation for 800 meters (1/2 mile) in all directions.

PUBLIC SAFETY MEASURES - EMERGENCY RESPONSE GUIDEBOOK, GUIDE 123 (ERG, 2004)

CALL Emergency Response Telephone Number on Shipping Paper first. If Shipping Paper not available or no answer, refer to appropriate telephone number:

MEXICO:

SETIQ:

01-800-00-214-00 in the Mexican Republic;
For calls originating in Mexico City and the Metropolitan Area: 5559-1588;
For calls originating elsewhere, call: 011-52-555-559-1588.

CENACOM:

01-800-00-413-00 in the Mexican Republic;
For calls originating in Mexico City and the Metropolitan Area: 5550-1496, 5550-1552, 5550-1485, or 5550-4885;
For calls originating elsewhere, call: 011-52-555-550-1496, or 011-52-555-550-1552; 011-52-555-550-1485, or 011-52-555-550-4885.

ARGENTINA:

CIQUIME:

0-800-222-2933 in the Republic of Argentina;
For calls originating elsewhere, call: +54-11-4613-1100.

BRAZIL:

PRÓ-QUÍMICA:

0-800-118270 (Toll-free in Brazil);
For calls originating elsewhere, call: +55-11-232-1144 (Collect calls are accepted).

COLUMBIA:

CISPROQUIM:

01-800-091-6012 in Colombia;
For calls originating in Bogotá, Colombia, call: 288-6012;
For calls originating elsewhere, call: 011-57-1-288-6012.

CANADA:

CANUTEC:

613-996-6666 (Collect calls are accepted);
*666 cellular (in Canada only).

UNITED STATES:

CHEMTREC®:

1-800-424-9300 (Toll-free in the U.S., Canada, and the U.S. Virgin Islands);
703-527-3887 for calls originating elsewhere (Collect calls are accepted).

CHEM-TEL, INC.:

1-800-255-3924 (Toll-free in the U.S., Canada, and the U.S. Virgin Islands);
813-248-0585 for calls originating elsewhere (Collect calls are accepted).

INFOTRAC:

1-800-535-5053 (Toll-free in the U.S., Canada, and the U.S. Virgin Islands);
352-323-3500 for calls originating elsewhere (Collect calls are accepted).

3E COMPANY:

1-800-451-8346 (Toll-free in the U.S., Canada, and the U.S. Virgin Islands);
760-602-8703 for calls originating elsewhere (Collect calls are accepted).

NATIONAL RESPONSE CENTER (NRC):

1-800-424-8802 - (24 hours) (Toll-free in the U.S., Canada, and the U.S. Virgin Islands);
202-267-2675 for calls in the District of Columbia.

MILITARY SHIPMENTS:

703-697-0218 - Explosives/ammunition incidents (Collect calls are accepted);
1-800-851-8061 - All other dangerous goods incidents.

NATIONWIDE POISON CONTROL CENTER (United States only):

1-800-222-1222 (Toll-free in the U.S.).

For additional details see the section entitled "WHO TO CALL FOR ASSISTANCE" under the ERG Instructions.
As an immediate precautionary measure, isolate spill or leak area for at least 100 meters (330 feet) in all directions.
Keep unauthorized personnel away.
Stay upwind.
Many gases are heavier than air and will spread along ground and collect in low or confined areas (sewers, basements, tanks).
Keep out of low areas.
Ventilate closed spaces before entering.

AIHA ERPG Values for CAS74-83-9 (AIHA, 2006):

Listed as Methyl Bromide
ERPG-1 (units = ppm): Not appropriate
ERPG-2 (units = ppm): 50
ERPG-3 (units = ppm): 200
Under Ballot, Review, or Consideration: No
Definitions:

ERPG-1: The ERPG-1 is the maximum airborne concentration below which it is believed nearly all individuals could be exposed for up to one hour without experiencing more than mild, transient adverse health effects or perceiving a clearly defined objectionable odor.
ERPG-2: The ERPG-2 is the maximum airborne concentration below which it is believed nearly all individuals could be exposed for up to one hour without experiencing or developing irreversible or other serious health effects or symptoms that could impair an individual's ability to take protective action.
ERPG-3: The ERPG-3 is the maximum airborne concentration below which it is believed nearly all individuals could be exposed for up to one hour without experiencing or developing life-threatening health effects.

DOE TEEL Values for CAS74-83-9 (U.S. Department of Energy, Office of Emergency Management, 2010):

Listed as Methyl bromide; (Bromomethane)
TEEL-0 (units = ppm): 1
TEEL-1 (units = ppm): 30
TEEL-2 (units = ppm): 210
TEEL-3 (units = ppm): 740
Definitions:

TEEL-0: The threshold concentration below which most people will experience no adverse health effects.
TEEL-1: The airborne concentration (expressed as ppm [parts per million] or mg/m(3) [milligrams per cubic meter]) of a substance above which it is predicted that the general population, including susceptible individuals, could experience notable discomfort, irritation, or certain asymptomatic, nonsensory effects. However, these effects are not disabling and are transient and reversible upon cessation of exposure.
TEEL-2: The airborne concentration (expressed as ppm or mg/m(3)) of a substance above which it is predicted that the general population, including susceptible individuals, could experience irreversible or other serious, long-lasting, adverse health effects or an impaired ability to escape.
TEEL-3: The airborne concentration (expressed as ppm or mg/m(3)) of a substance above which it is predicted that the general population, including susceptible individuals, could experience life-threatening adverse health effects or death.

AEGL Values for CAS74-83-9 (National Research Council, 2010; National Research Council, 2009; National Research Council, 2008; National Research Council, 2007; NRC, 2001; NRC, 2002; NRC, 2003; NRC, 2004; NRC, 2004; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2006; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2007; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2005; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2005; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2007; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2006; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2006; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2006; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2006; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2006; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2006; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2006; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2006; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2006; United States Environmental Protection Agency Office of Pollution Prevention and Toxics, 2006; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2006; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2007; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2007; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2007; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2007; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2007; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2009; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2009; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2009; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2009; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2009; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2009; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2009; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2009; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2009; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2009; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2009; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2009; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2009; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2007; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2006; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2006; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2006; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2007; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2007; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2007; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2007; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2007; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2005; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2005; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2005; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2005; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2005; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2005; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2005; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2005; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2007; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2005; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2006; 62 FR 58840, 1997; 65 FR 14186, 2000; 65 FR 39264, 2000; 65 FR 77866, 2000; 66 FR 21940, 2001; 67 FR 7164, 2002; 68 FR 42710, 2003; 69 FR 54144, 2004):

Not Listed

NIOSH IDLH Values for CAS74-83-9 (National Institute for Occupational Safety and Health, 2007):

IDLH: 250 ppm
Note(s): Ca

(Ca) NIOSH considers this substance to be a potential occupational carcinogen (See Appendix A).

CONTAINMENT/WASTE TREATMENT OPTIONS

SUMMARY

SPILL OR LEAK PRECAUTIONS - EMERGENCY RESPONSE GUIDEBOOK, GUIDE 123 (ERG, 2004)
- Fully encapsulating, vapor protective clothing should be worn for spills and leaks with no fire.
- Do not touch or walk through spilled material.
- Stop leak if you can do it without risk.
- If possible, turn leaking containers so that gas escapes rather than liquid.
- Prevent entry into waterways, sewers, basements or confined areas.
- Use water spray to reduce vapors or divert vapor cloud drift. Avoid allowing water runoff to conact spilled material.
- Do not direct water at spill or source of leak.
- Isolate area until gas has dispersed.
RECOMMENDED PROTECTIVE CLOTHING - EMERGENCY RESPONSE GUIDEBOOK, GUIDE 123 (ERG, 2004)
- Wear positive pressure self-contained breathing apparatus (SCBA).
- Wear chemical protective clothing that is specifically recommended by the manufacturer. It may provide little or no thermal protection.
- Structural firefighters' protective clothing provides limited protection in fire situations ONLY; it is not effective in spill situations where direct contact with the substance is possible.
Spills involving methyl bromide may require isolation of spilled material or evacuation of personnel. Approach spill from upwind. Stop or control the leak, if possible. Leaking cylinders should be moved to a well-ventilated location or a safe outdoor location. Containers should be vented slowly (Sittig, 1991). Water spray may be used to cool and disperse vapors and protect personnel. Runoff should be controlled and isolated for proper disposal (NFPA, 1997). Spilled material should be kept out of water sources, sewers, confined areas, and basements. Dikes may be used to contain flow (AAR, 1996). Methyl bromide may be absorbed by organic solvents (toluene, carbon tetrachloride, chloroform, and ethyl alcohol). The solution should then be disposed of properly (CGA, 1990).
If methyl bromide is spilled on land, pits, ponds, lagoons, or other holding areas may be used to contain spilled material. If possible, holding areas should be sealed with an impermeable, flexible membrane liner. Surface flow may be diked using soil, sand bags, foamed polyurethane, or foamed concrete. Bulk liquid may be absorbed using fly ash or cement powder (HSDB , 1999).
If methyl bromide is spilled in water, natural deep water pockets, excavated lagoons, or sand bag barriers may be used to trap compound at the bottom. If compound is dissolved, in a region of 10 ppm or greater, activated carbon (10 times the spilled amount) may be applied. Mechanical dredges or lifts may be used to remove immobilized masses of the compound and precipitates (HSDB , 1999).
If methyl bromide is spilled in the air, water spray may be used to knock down the vapors (HSDB , 1999).

WASTE TREATMENT OPTIONS

PHYSICAL TREATMENT

Methyl bromide is a potential candidate for rotary kiln incineration at a temperature range of 820 to 1600 degrees 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 degrees C and residence times of seconds for liquids and gases, and longer for solids (HSDB , 1999).
Methyl bromide gas should be sprayed into a fire box of an incinerator that is equipped with an afterburner and an alkali scrubber (Sittig, 1991).
Venting is not recommended. Methyl bromide should be poured into vermiculite, sodium bicarbonate, or sand-soda ash mixture (90/10). Slaked lime may be added if fluoride is present. Then, it should be mixed in paper boxes and placed in an incinerator. Cover boxes with scrap wood and paper and ignite with excelsior train (OHM/TADS , 1999).
Waste management activities associated with material disposition are unique to individual situations. Proper waste characterization and decisions regarding waste management should be coordinated with the appropriate local, state, or federal authorities to ensure compliance with all applicable rules and regulations.

-ENVIRONMENTAL HAZARD MANAGEMENT

POLLUTION HAZARD

Methyl bromide occurs naturally in the environment from oceanic biological activity, particularly seaweed. Also, methyl bromide is released to the environment from its use as a soil and space fumigant and its occurrence in automobile exhaust (Clayton & Clayton, 1994; Howard, 1989).

ENVIRONMENTAL FATE AND KINETICS

Methyl bromide released into the atmosphere is expected to react with photochemically generated hydroxyl radicals (half-life from 0.29 years to 1.6 years). In the troposphere, direct photolysis is not expected to be important, but upward diffusion is the dominant loss mechanism. In the stratosphere, photolysis is the primary removal process. The estimated atmospheric residence time is 289 days (Howard, 1989). Howard (1991) reports half-lives of 68-680 days.

WATER

SURFACE WATER
- In water, volatilization is expected to be the primary removal mechanism (half-life 3 hours in a model river). "Hydrolysis to methanol and bromide ions will occur with a half-life of 20-26.7 days." Methyl bromide is not expected to bioconcentrate in fish (Howard, 1989). In surface water, Howard (1991) reports half-lives of 7 days to 4 weeks. In ground water, half-lives are 14-38 days.

SOIL

TERRESTRIAL
- In soil, volatilization is the primary fate process. Methyl bromide is expected to have weak adsorption to soil and is expected to leach into ground water (Howard, 1989). Hydrolysis may occur in neutral and alkaline soils, resulting in the production of methanol and bromide ions (HSDB , 1999). "Degradation is by hydrolysis which is soil catalyzed and is much faster in peat soil than in loam, and in loam than in sand" (Howard, 1989). Howard (1991) reports half-lives of 7 days to 4 weeks.

ABIOTIC DEGRADATION

Hydrolysis rates for methyl bromide (at 25 degrees C and pH 7) are 4.09x10(-7) (half-life of 20 days) and 3x10(-7) (half-life of 26.7 days). In the gas phase, the half-lives for the reaction of methyl bromide with hydroxyl radicals are (Howard, 1989):

5x10(5) molecules/cm(3) -- 1.6 years (at -8 degrees C); 1.1 years (at 25 degrees C)
1x10(6) molecules/cm(3) -- 0.79 years (at -8 degrees C); 0.57 years (at 25 degrees C)
2x10(6) molecules/cm(3) -- 0.40 years (at -8 degrees C); 0.29 years (at 25 degrees C)

BIODEGRADATION

Methyl bromide is oxidized by methylotrophic bacteria (Howard, 1989).

BIOACCUMULATION

BIOCONCENTRATION FACTOR

Based on a measured log octanol/water partition coefficient of 1.19, methyl bromide has a bioconcentration factor of 4.7 (Howard, 1989).

ENVIRONMENTAL TOXICITY

Ecotoxicity Values (HSDB , 1999)

LC50 - Lepomis macrochirus\Bluegill: 11 ppm for 96H -- static bioassay, fresh water (at 23 degrees C), mild aeration applied after 24H
LC50 - Menidia beryllina\tidewater silverside: 12 ppm for 96H -- static bioassay in synthetic seawater (at 23 degrees C), mild aeration applied after 24H
LD50 - Coleoptera: 4.505 mg/L for 24H

TERMITES: The susceptibility of 10 species of termites to toxic exposures of methyl bromide was measured at 27 degrees C. The LC50 and LC99 values were measured and the following lethal doses found (Scheffrahn & Su, 1992):

LC50 - R. HESPERUS PSEUDERGATES: 11.4 mg/L for 1H
LC50 - C. CAVIFRONS PSEUDERGATES: 45.9 mg/L for 1H
LC99 - R. HESPERUS PSEUDERGATES: 16.5 mg/L for 1H
LC99 - C. CAVIFRONS PSEUDERGATES: 75.0 mg/L for 1H

The effect of methyl bromide (CH3Br) in admixtures with varying concentrations of carbon monoxide (CO) on Tribolium castaneum was evaluated. The combination of CH3Br with CO showed an increase in CH3Br toxicity; 1.4 fold increase with 20% CO, 1.5 fold increase with 30% CO, and 1.7 fold increase with 40% CO. The report suggests that it is the inhibitory effect of CO on the insect's microsomal mixed-function oxidase system that causes this effect (Calderon, 1992).

-PHYSICAL/CHEMICAL PROPERTIES

MOLECULAR WEIGHT

Methyl bromide: 94.94

DESCRIPTION/PHYSICAL STATE

Methyl bromide is a colorless, transparent, easily liquified gas or volatile liquid with a burning taste and a sweetish, chloroform-like odor at high concentrations (Bingham et al, 2001; Lewis, 1996; Budavari, 1996). It is a gas at ordinary temperatures with no warning properties (Clayton & Clayton, 1996). At low vapor concentration, methyl bromide is not detectable by taste or odor. In ice water, methyl bromide forms a crystalline hydrate (HSDB , 2001).

VAPOR PRESSURE

1250 mmHg (at 20 degrees C) (NFPA, 1997)

1250 mmHg (at 25 degrees C) (Lewis, 1997)

1420 mmHg (at 20 degrees C) (Budavari, 1996)

1620 mmHg (at 25 degrees C) (HSDB , 2001)

1.9 atm (NIOSH , 1999)

27.5 psig; 189.6 kPa (at 21.1 degrees C; 70 degrees F) (CGA, 1990)

50.0 psig; 344.7 kPa (at 40.6 degrees C; 105 degrees F) (CGA, 1990)

58.5 psig; 405.3 kPa (at 46.1 degrees C; 115 degrees F) (CGA, 1990)

74.0 psig; 510.2 kPa (54.4 degrees C; 130 degrees F) (CGA, 1990)

SATURATED VAPOR PRESSURE

27.710 lb/in(2) (at 70 degrees F) (HSDB , 2001)

SPECIFIC GRAVITY

NORMAL TEMPERATURE AND PRESSURE

(25 degrees C; 77 degrees F and 760 mmHg)
GAS: 3.355 (at 25 degrees C; 1 atm) (CGA, 1990)

STANDARD TEMPERATURE AND PRESSURE

(0 degrees C; 32 degrees F and 760 mmHg)
LIQUID: 1.732 (at 0/0 degrees C) (Lewis, 1996)
LIQUID: 1.730 (at 0/4 degrees C) (Budavari, 1996)

OTHER TEMPERATURE AND/OR PRESSURE

LIQUID: 1.68 (at 20 degrees C) (ACGIH, 1991)
VAPOR: 3.974 g/L (at 20 degrees C) (ITI, 1995)

TEMPERATURE AND/OR PRESSURE NOT LISTED

LIQUID: 1.7 (NFPA, 1997)
LIQUID: 1.73 (NFPA, 1997)
VAPOR: 3.3 g/L (CHRIS , 1999)

DENSITY

NORMAL TEMPERATURE AND PRESSURE

(25 degrees C; 77 degrees F and 760 mmHg)
LIQUID: 1662 kg/m(3); 103.75 lb/ft(3) (at 25 degrees C; 77 degrees F) (CGA, 1990)

OTHER TEMPERATURE AND/OR PRESSURE

GAS: 3.974 g/L (at 20 degrees C) (Budavari, 1996)
LIQUID: 1.732 (at 0 degrees C) (Lewis, 1997)
LIQUID: 1.73 kg/L (at 20 degrees C) (Ashford, 1993)
LIQUID: 1676 kg/m(3); 104.63 lb/ft(3) (at 20 degrees C; 68 degrees F) (CGA, 1990)
LIQUID: 1660 kg/m(3); 103.63 lb/ft(3) (at 40 degrees C; 104 degrees F) (CGA, 1990)
LIQUID: 1660 kg/m(3); 99.88 lb/ft(3) (at 60 degrees C; 140 degrees F) (CGA, 1990)
LIQUID: 1555 kg/m(3); 97.07 lb/ft(3) (at 80 degrees C; 176 degrees F) (CGA, 1990)

SATURATED VAPOR DENSITY

0.46270 lb/ft(3) (at 70 degrees F) (HSDB , 2001)

FREEZING/MELTING POINT

FREEZING POINT

-93 degrees C (Lewis, 1996)
-94 degrees C (Lewis, 1997)

MELTING POINT

-93.66 degrees C (Budavari, 1996)
-93 degrees C; -135 degrees F; 180 degrees K (CHRIS , 1999; NFPA, 1997)
-94 degrees C; 137.2 degrees F (CGA, 1990; EPA, 1988)
-137 degrees F (NIOSH , 1999)

BOILING POINT

38 degrees F (NIOSH , 1999)

3.56 degrees C; 38.4 degrees F (Budavari, 1996; CGA, 1990; Lewis, 1997)

3.46 degrees (CLewis, 1993)

3.55 degrees C (HSDB , 2001)

3.6 degrees C; 38.5 degrees F; 276.8 degrees K (CHRIS , 1999; Clayton & Clayton, 1994)

4 degrees C; 38.4 degrees F (NFPA, 1997)

4 degrees C; 39 degrees F (NFPA, 1997)

4.5 degrees C (ITI, 1995)

FLASH POINT

None (Lewis, 1996; NIOSH , 1999)

AUTOIGNITION TEMPERATURE

998 degrees F (Lewis, 1996)

537 degrees C; 999 degrees F (Clayton & Clayton, 1994; NFPA, 1997)

EXPLOSIVE LIMITS

LOWER

10% (ACGIH, 1991; NFPA, 1997)
13.5% (Lewis, 1997)

UPPER

14.5% (Lewis, 1997)
15% (ACGIH, 1991)
16% (NFPA, 1997)

SOLUBILITY

IN WATER

1.75 g/100 g of solution (20 degrees C, 748 mm Hg) (Budavari, 1996)
0.09 g/100 mL water (20 degrees C) (Clayton & Clayton, 1994)
13.4 g/kg water (25 degrees C) (HSDB , 2001)
15200 mg/L water (at 25 degrees C) (HSDB , 2001)
900 mg/L water (at 20 degrees C) (HSDB , 2001)
Methyl bromide is not soluble in water (NFPA, 1997).
Methyl bromide forms a voluminous crystalline hydrate (CH3Br.2OH2O) below 4 degrees C (Budavari, 1996; Lewis, 1997).

IN ORGANIC SOLVENTS

Methyl bromide is freely soluble in alcohol, chloroform, ether, carbon disulfide, carbon tetrachloride, and benzene (Budavari, 1996). It is also soluble in ethanol and ethyl ether (Clayton & Clayton, 1994; HSDB , 2001).
Methyl bromide is miscible with most organic solvents (Lewis, 1993).
>10% in ethanol (HSDB , 2001)
>10% in chloroform (HSDB , 2001)

OCTANOL/WATER PARTITION COEFFICIENT

log Kow = 1.19 (HSDB , 2001)

HENRY'S CONSTANT

5.26x10(-3) atm-m(3)/mol (Ehrenfeld et al, 1986)

6.24x10(-3) atm-m(3)/mol (Howard, 1989; HSDB , 2001)

SPECTRAL CONSTANTS

10972 (Sadtler Research Laboratories IR Grating Collection) (HSDB , 2001)

5-2 (Organic Electronic Spectral Dat Phillips et al, John Wiley & Sons) (HSDB , 1999)

MASS

195 (Atlas of Mass Spectral Data, John Wiley & Sons) (HSDB , 2001)

OTHER/PHYSICAL

ODOR THRESHOLD

LOW: 80 mg/m(3) (HSDB , 2001)
HIGH: 4000 mg/m(3) (HSDB , 2001)

SURFACE TENSION

24.5 dynes/cm; 0.0245 N/m (at 15 degrees for the liquid) (CHRIS , 1999)

CRITICAL PRESSURE

5220 kPa abs; 757.1 psia (CGA, 1999)
83.4 atm (HSDB , 2001)

CRITICAL TEMPERATURE

194 degrees C; 381.2 degrees F (Budavari, 1996; CGA, 1990)
191 degrees C; 376 degrees F; 464 degrees K (CHRIS , 1999)

HEAT OF COMBUSTION

-3188 Btu/lb; -1771 cal/g; 74.15x10(5) J/kg (CHRIS , 1999)

HEAT OF FUSION

15.05 cal/g; 62.97 J/g; 5978 J/mol (CHRIS , 1999; HSDB , 2001)

INDEX OF REFRACTION

1.4432 (at -20 degrees C) (Budavari, 1996)
1.4218 (at 20 degrees C) (HSDB , 2001)

IONIZATION POTENTIAL

10.54 eV (NIOSH , 1999)

VISCOSITY

0.397 (closed cup) (at 0 degrees C) (Budavari, 1996)
0.22 centistokes (at 0 degrees C) (HSDB , 2001)

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METHYL BROMIDE

Classification | Information to evaluate chemical incidents

Information to evaluate chemical incidents

Information to evaluate chemical incidents

Information to evaluate chemical incidents