Bromomethane
Bromomethane, commonly known as methyl bromide, is an organobromine compound with formula CH3Br. This colorless, odorless, nonflammable gas is produced both industrially and biologically. It has a tetrahedral shape and it is a recognized ozone-depleting chemical. It was used extensively as a pesticide until being phased out by most countries in the early 2000s.
Occurrence and manufacture
Bromomethane originates from both natural and human sources. In the ocean, marine organisms are estimated to produce 56,000 tonnes annually. It is also produced in small quantities by certain terrestrial plants, such as members of the family Brassicaceae. It is manufactured for agricultural and industrial use by treating methanol with bromine in the presence of sulfur or hydrogen sulfide:Uses
In 1999, an estimated 71,500 tonnes of synthetic methyl bromide were used annually worldwide. 97% of this estimate was used for fumigation purposes, whilst 3% was used for the manufacture of other products. Moreover, 75% of the consumption used to take place in developed nations, led by the United States and Europe. Asia and the Middle East combined to use 24% whereas Latin America and Africa had the lowest usage at 9%.markings on a pallet from China. The MB indicates the wood has been fumigated with methyl bromide to kill pests.
Until its production and use was curtailed by the Montreal Protocol, bromomethane was widely applied as a soil sterilant, mainly for production of seed but also for some crops such as strawberries and almonds. In commercial large-scale monoculture seed production, unlike crop production, it is of vital importance to avoid contaminating the crop with off-type seed of the same species. Therefore, selective herbicides cannot be used. Although bromomethane is dangerous, it is considerably safer and more effective than some other soil sterilants. Its loss to the seed industry has resulted in changes to cultural practices, with increased reliance on soil steam sterilization, mechanical rogueing, and fallow seasons. Bromomethane was also used as a general-purpose fumigant to kill a variety of pests including rats and insects. Bromomethane has poor fungicidal properties. Bromomethane is the only fumigant allowed under ISPM 15 regulations when exporting solid wood packaging to ISPM 15 compliant countries. Bromomethane is used to prepare golf courses, particularly to control Bermuda grass. The Montreal Protocol stipulates that bromomethane use be phased out.
Bromomethane is also a precursor in the manufacture of other chemicals as a methylating agent.
Bromomethane was once used in specialty fire extinguishers, prior to the advent of less toxic halons, as it is electrically non-conductive and leaves no residue. It was used primarily for electrical substations, military aircraft, and other industrial hazards. It was never as popular as other agents due to its high cost and toxicity. Bromomethane was used from the 1920s to the 1960s, and continued to be used in aircraft engine fire suppression systems into the late 1960s.
Regulation
Bromomethane is readily photolyzed in the atmosphere to release bromine radicals, which are far more destructive to stratospheric ozone than chlorine. As such, it is subject to phase-out requirements of the 1987 Montreal Protocol on Ozone Depleting Substances.The London Amendment in 1990 added bromomethane to the list of ODS to be phased out. In 2003 the Global Environment Facility approved funds for a UNEP-UNDP joint project for methyl bromide total sector phase out in seven countries in Central Europe and Central Asia, which was due for completion in 2007.
Alternatives
Alternatives to bromomethane in the agricultural field are currently in use and further alternatives are in development, including propylene oxide and furfural.Australia
In Australia, bromomethane is the preferred fumigant of the Department of Agriculture and Water Resources for most organic goods imported into Australia. The department conducts methyl bromide fumigation certification for both domestic and foreign fumigators who can then fumigate containers destined for Australia. A list of alternative fumigants is available for goods imported from Europe, where methyl bromide fumigation has been banned. Alternatively, the department allows containers from Europe to be fumigated with methyl bromide on arrival to Australia.New Zealand
In New Zealand, bromomethane is used as a fumigant for whole logs destined for export. Environmental groups and the Green Party oppose its use. In May 2011 the Environmental Risk Management Authority introduced new rules for its use which restrict the level of public exposure to the fumigant, set minimum buffer zones around fumigation sites, provide for notification to nearby residents and require users to monitor air quality during fumigations and report back to ERMA each year. All methyl bromide fumigations must use recapture technology by 2021.United States
In the United States bromomethane is regulated as a pesticide under the Federal Insecticide, Fungicide, and Rodenticide Act and as a hazardous substance under the Resource Conservation and Recovery Act, and is subject to reporting requirements under the Emergency Planning and Community Right-to-Know Act. The U.S. Clean Air Act. A 1998 amendment conformed the Clean Air Act phase out date with that of the Montreal Protocol. Whereas the Montreal Protocol has severely restricted the use of bromomethane internationally, the United States has successfully lobbied for critical-use exemptions. Critical use exemptions allow the United States to continue using MeBr until it is scheduled to be completely phased out sometime in 2017.In 2004, over 7 million pounds of bromomethane were applied in California. Applications include tomato, strawberry, and ornamental shrub growers, and fumigation of ham/pork products. Also exempt is the treatment of solid wood packaging, and the packaged goods, being exported to ISPM 15 countries.
Chile
Has phased out the use in traditional agriculture on 2015, with exemption of the 100% pure formulation that is continued and largely used for quarantine pest control and at pre-shipments of the fruit export industry.Health effects
Brief exposure to high concentrations and prolonged inhalation of lower concentrations are problematic. Exposure levels leading to death vary from 1,600 to 60,000 ppm, depending on the duration of exposure. Concentrations in the range of 60,000 ppm can be immediately fatal, while toxic effects can present following prolonged exposure to concentrations well under 1,000 ppm."A TLV–TWA of 1 ppm is recommended for occupational exposure to methyl bromide"-ACGIH 8 hour time weighted average. Immediately Dangerous To Life or Health Concentration by NIOSH: "The revised IDLH for methyl bromide is 250 ppm based on acute inhalation toxicity data in humans . This may be a conservative value due to the lack of relevant acute toxicity data for workers exposed to concentrations above 220 ppm. " Detectable concentration by Drager Tube is 0.5 ppm.
Respiratory, kidney, and neurological effects are of the greatest concern.
Treatment of wood packaging requires a concentration of up to 16,000 ppm.
NIOSH considers methyl bromide to be a potential occupational carcinogen as defined by the OSHA carcinogen policy . "Methyl bromide showed a significant dose-response relationship with prostate cancer risk."