Methyl bromide stratospheric reactions

Due to its gaseous nature it may have an effect on the stratospheric ozone layer [281, 402, 404]. After injection into soil for fumigation, methyl bromide rapidly diffuses through the soil pore space to the soil surface and then into the atmosphere [159,162,163,405,406]. Since a plastic sheet typically covers the soil surface, the rate of emission into the atmosphere depends upon the thickness and density of the plastic, if other conditions are the same [159, 406]. Other routes of disappearance from soil include chemical hydrolysis, methylation to soil organic matter through free radical reactions, and microbial degradation [ 136,159,405,407]. Several reports appeared on the study of the microbial transformations of methyl bromide, summarized as follows ... 

These data also demonstrate the impact of bromine chemistry on the stratosphere (see Chapter 12.D). The initial ODP for methyl bromide is 15, due primarily to the large a factor associated with bromine chemistry. However, since it is removed by reaction with OH in the troposphere as well as by other processes such as hydrolysis in the oceans and uptake by soils and foliage (see Chapter 12.D), it has a short atmospheric lifetime of 1.3 years and hence the ODP decreases rapidly with time, toward a long-term steady-state value. 

For some pesticide compounds, such as dini-troaniline herbicides (Weber, 1990), phototransformation occurs primarily in the vapor phase, rather than in the dissolved or sorbed phases. Perhaps the most environmentally significant pesticide phototransformation in the atmosphere, however, is the photolysis of the fumigant methyl bromide, since the bromine radicals created by this reaction are 50 times more efficient than chlorine radicals in destroying stratospheric ozone (Jeffers and Wolfe, 1996). Detailed summaries of the rates and pathways of phototransformation of pesticides and other organic compounds in natural systems, and discussions of the physical and chemical factors that influence these reactions, have been presented elsewhere (e.g., Zepp et al, 1984 Mill and Mabey, 1985 Harris, 1990b). 

Other substances that can find their way into the stratosphere can increase the rate of ozone depletion as well. Halons, which are compounds consisting of bromine, fluorine, and carbon, can end up in the upper atmosphere where the halogens found in the compounds catalyze the ozone consuming reactions. Methyl bromide... 

Bromine is potentially able to interact with stratospheric ozone in the same manner as chlorine (Wofsy et al., 1975). The catalytic cycle for bromine is expected to be quite efficient, because its reaction with methane is slower than that of Cl atoms in addition, the reaction of OH with HBr is faster than that of OH with HC1. The major bromine compound in the troposphere is methyl bromide, which has a natural origin and occurs with a mixing ratio of about 10 pptv (see Table 6-14). This seems small enough to neglect bromine to a first approximation. 

As with methyl chloride, large quantities of methyl bromide, CH3Br, are also produced naturally and some of it eventually reaches the stratosphere, where it decomposes photochemically to yield atomic bromine. Like chlorine, bromine atoms can destroy ozone by the mechanism shown in reactions (5) and (6). These reactions are as follows ... 

PROBABLE FATE photolysis volatilized methyl bromide should photodissociate above the ocean layer, probably not significant in aquatic systems, reaction with photochemi-cally produced hydroxyl radicals has a half-life from 0.29-1.6 yrs, direct photolysis is the dominant fate in the stratosphere, but is not expected to be important in the troposphere oxidation atmospheric photooxidation by hydroxyl radicals releases inorganic bromide which is carried... 

In the 1970s, scientists linked several man-made substances to ozone depletion, including carbon tetrachloride (CCE), chlorofluorocarbons (CFCs), halons, methyl bromide, and methyl chloroform. These chemicals leak from air conditioners, refrigerators, insulating foam, and some industrial processes. Winds carry them through the lower atmosphere into the stratosphere, where they react with strong solar radiation to release chlorine and bromine atoms. These atoms initiate chain reactions that consiune ozone. Scientists estimate that a single chlorine atom can destroy 100,000 ozone molecules. 

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