Depleting methyl bromide residues in soil by reaction with bases

Despite generally being considered the most effective soil fumigant, methyl bromide (MeBr) use is being phased out because its emissions from soil can lead to stratospheric ozone depletion. However, a large amount is still currently used due to Critical Use Exemptions. As strategies for reducing the postfumigation emissions of MeBr from soil, Ca(OH)(2), K(2)CO(3), and NH(3) were assessed as means of promoting MeBr degradation. Ammonia aqueous solution (NH(4)OH) was the most effective, because MeBr can be degraded by both hydrolysis and ammonolysis. At 20 °C, the half-lives (t(1/2)) of MeBr were 18.0, 2.5, and 1.3 h in 0.1, 1.0, and 2.0 M NH(4)OH, respectively. In 1.0 M NH(4)OH, increasing the solution temperature to 40 °C reduced the half-life of MeBr to 0.23 h. Ammonia amendment to moist soil also promoted MeBr transformation, and the MeBr degradation rate increased with increasing soil temperature. NH(4)OH (30%, 16 M) very effectively reacted with MeBr that was contained under plastic film. Under Hytibar (a virtually impermeable film, VIF), over 99.5% of the MeBr could be destroyed by 30% NH(4)OH in 8 h at 20 °C. On the basis of these results, good management practices (i.e., VIF plus NH(4)OH) could be developed for continued use of MeBr as a soil fumigant under Critical Use Exemptions, without significant emissions.     

Reactive films for mitigating methyl bromide emissions from fumigated soil

Emissions of methyl bromide (MeBr) from agricultural fumigation can lead to depletion of the stratospheric ozone layer, and so its use is being phased out. However, as MeBr is still widely used under Critical Use Exemptions, strategies are still required to control such emissions. In this work, novel reactive films (RFs) were designed and their efficacy in limiting loss of MeBr from soil was tested. A reactive layer, containing dry ammonium thiosulfate (ATS), was sandwiched between two layers of plastic film, the lower layer being HDPE (high-density polyethylene film, which is permeable to MeBr) and the upper layer HDPE or VIF (virtually impermeable film). MeBr diffusion through, and transformation by, the RFs were tested in a stainless-steel permeability cell. Although ineffective when dry, the RFs substantially depleted MeBr when activated with water to produce ATS solution. MeBr half-life (t(1/2)) was around 9.0 h at 20 °C in the presence of activated RF, and was sensitive to temperature (t(1/2) 15.7 and 2.9 h at 10 and 40 °C, respectively). When the upper film layer was VIF, less than 0.15% of the added MeBr diffused through the film, with the remainder being transformed within the reactive layer. These findings indicate that such films have good potential to reduce MeBr loss from fumigated soils to the atmosphere.     

Residues after fumigation with methyl bromide: bromide ion and methyl bromide in middlings and final cereal foodstuffs

Methyl bromide and bromide ion concentrations were estimated in pasta manufactured before and after fumigation with methyl bromide. The first trial estimated the bromide ion concentrations in fumigated and unfumigated flours and in pastas obtained from these. The concentration of bromide ions in fumigated flours was not significantly different from unfumigated flours. Only some pastas, manufactured from fumigated flours, showed a higher bromide ion concentration than those manufactured from unfumigated flours. The second trial evaluated the bromide ion concentrations of rices, white flours, flours, pastas made only from flours, pastas with eggs and pastas with eggs and spinach, before and after exposure to methyl bromide in their retail packagings. The bromide ion concentrations in fumigated pastas with eggs, pastas with eggs and spinach and rice were higher than in those unfumigated. In the pastas with eggs the bromide ion concentration after fumigation increased ten times (from about 4 to 40 mg/kg). Results showed that the bromide ion and methyl bromide levels estimated in all the foodstuffs examined were lower than the maximum limits fixed by several different national regulations.     

The fumigation of white sugar in packets with methyl bromide

Methyl bromide was found to penetrate into single wrapped 454 g packets and 12·7 kg (28 lb) packages of sugar effectively and to be well distributed in large stacks under gas-proof sheets during a 24 hr fumigation. Gas concentrations, as determined by thermal conductivity meter and by gas chromatography using a micro-sampling technique for individual packages, showed that a dose of 24 g per m³ (24 oz per 1000 ft³) should be sufficient to control insects in a 24 hr fumigation.     

Bioreactors for removing methyl bromide following contained fumigations

Use of methyl bromide (MeBr) as a quarantine, commodity, or structural fumigant is under scrutiny because its release to the atmosphere contributes to the depletion of stratospheric ozone. A closed-system bioreactor consisting of 0.5 L of a growing culture of a previously described bacterium, strain IMB-1, removed MeBr (> 110 micromol L(-1)) from recirculating air. Strain IMB-1 grew slowly to high cell densities in the bioreactor using MeBr as its sole carbon and energy source. Bacterial oxidation of MeBr produced CO2 and hydrobromic acid (HBr), which required continuous neutralization with NaOH for the system to operate effectively. Strain IMB-1 was capable of sustained oxidation of large amounts of MeBr (170 mmol in 46 d). In an open-system bioreactor (10-L fermenter), strain IMB-1 oxidized a continuous supply of MeBr (220 /micromol L(-1) in air). Growth was continuous, and 0.5 mol of MeBr was removed from the air supply in 14 d. The specific rate of MeBr oxidation was 7 x 10(-16) mol cell(-1) h(-1). Bioreactors such as these can therefore be used to remove large quantities of contaminant MeBr, which opens the possibility of biodegradation as a practical means for its disposal.     

Site of decomposition of methyl bromide in cocoa beans

The main site of decomposition of methyl bromide in cocoa beans was shown to be in the alcohol-insoluble proteins of the shells. The methyl group of the fumigant becomes covalently bonded to the α-amino group of the various amino acids, the imidazole ring of histidine and the ε-amino group of lysine. An amino acid analysis of cocoa beans shows that methionine is the limiting essential amino acid and that cysteine is concentrated in the alcohol-insoluble proteins of the nib.     

Development of a methyl bromide collection system for fumigated farmland

Recent research has indicated that up to 73% of the methyl bromide (MeBr) applied to agricultural farmland is ultimately emitted to the atmosphere despite the practice of complete coverage of the fields with polyethylene (PE) tarp. To reduce the emission of MeBr, several techniques have been investigated. An alternative that has received little consideration is the collection and recycle or treatment of MeBr emissions. We investigated the potential of using a two-layer tarp system for collecting the MeBr. Laboratory experiments with a small two-layer diffusion reactor were conducted to determine the mass transfer coefficient (K) of MeBr through tarps and to validate a model of the collection system. For PE tarps K was 1.15 x 10(-6) m s-1 at 20 degrees C and 5.2 x 10(-6) m s-1 at 60 degrees C. K for so-called virtually impermeable films ranged from 4.6 x 10(-10) m s-1 to 1.3 x 10(-8) m s-1. The mathematical model was then used to simulate a full scale fumigant field application. Results indicate excellent agreement between the model, laboratory experiments, and previous field studies. Total emission from the field was a function of the air exchange rate through the swept volume between the two layers, the length of time the field is covered by the collection system, and the mass transfer coefficient of MeBr though the tarps. The results indicate that the proposed two-layer system can be very effective in collecting MeBr emissions from fumigated farmland.     

Fumigation trials with a mixture of methyl bromide and carbon dioxide in vertical bins

The efficacy of a fumigant mixture containing methyl bromide and carbon dioxide was examined using the gravity penetration method in vertical bins of wheat. When applied as the mixture methyl bromide penetrated to the bottom of the bins and complete control of test insects at the base of the bins as well as the existing natural infestation was obtained. Methyl bromide applied alone under similar conditions was not detected at the bottom of the bins and the insects of the natural infestation, and test insects remained alive. It is assumed the carbon dioxide acted as a carrier and facilitated the penetration of the methyl bromide to the depth of 17 m through the grain bulk.     

The effect of methyl bromide on esterase activity in wheat

Fumigation of wheat with methyl bromide causes a change in the polyacrylamide gel, isoelectric focusing profile of esterase proteins from aqueous extracts of wheat. The significance of this effect is discussed in the light of known reactions of methyl bromide in stored products.     

Measuring simultaneous production and consumption fluxes of methyl chloride and methyl bromide in annual temperate grasslands

Methyl chloride (CH3Cl) and methyl bromide (CH3Br) are both produced and consumed by terrestrial ecosystems, but large uncertainties remain about the magnitude of their emission and uptake rates. Most field-based studies report net fluxes, but knowledge of gross fluxes is required to assess partial atmospheric lifetimes and potential mechanisms. Here, we present the first field results using a stable isotope tracer technique to determine gross emission and uptake fluxes of CH3Cl and CH3Br at two temperate annual grasslands in California. These grasslands generally showed modest emission and uptake rates of CH3Cl and CH3Br, although large net emissions were observed at riparian and dry playa sites within these grasslands. While gross production rates of the methyl halides are not correlated to each other, gross consumption rates of CH3Cl and CH3Br show a molar uptake ratio of approximately 40: 1, consistent with results from other biomes. Gross consumption rates appear to be strongly affected by soil moisture. Temperate grassland soils have been previously identified as a globally significant sink for CH3Br, accounting for approximately 25% of the total soil sink, but our results suggest that the uptake rate could be much smaller.     

Predicted gas loss of sulfuryl fluoride and methyl bromide during structural fumigation

Elimination of insects in grain-milling facilities requires the periodic use of a gaseous insecticide (fumigant) that can destroy pests. Ideally, the fumigant concentration within a treated building should remain constant during the fumigation process to enhance efficacy while minimizing the amount of fumigant required. However, fumigant is often slowly lost through cracks and crevices within the structure. Wind impact on this leakage loss and in natural ventilation is explored using computational fluid dynamics (CFD). Two surrogate enclosure geometries, based on actual commercial grain mills, are used in the analysis. Building materials are assumed impermeable to fumigants, and cracks within structures are approximated as square regions where permeability parameters can be specified (i.e., porous jumps). Half-loss times (HLT) for sulfuryl fluoride (SF) and methyl bromide (MB) within the structure can be simulated. When diffusion dominates (no wind), SF had increased leakage rates of ∼5.4% over MB. However, simulated HLT due to diffusion are in the order of years for both fumigants. If the wind is blowing at measurable rates, convection-driven losses dominate and leakage from the mill is independent of the fumigant being used. Predicted half-loss times for MB and SF are statistically indistinguishable for external wind velocities from 0.125to 8 m s^-1. Therefore, HLTs are insensitive to fumigant physicochemical properties when the wind is blowing. Representative and diverse wind-frequency analysis for California and Texas show limited intervals of calm wind periods, and median wind speeds at or above those investigated in this analysis. Thus, decisions for product use should be based on efficacy, cost, and environmental impact, since convective-induced leakage rates are similar.     

Tolerance of the diapausing stages of four species of Lepidoptera to methyl bromide

The diapausing stages exposed to methyl bromide were larvae of Ephestia elutella (Hübner) and Plodia interpunctella (Hübner), pupae of Pieris brassicae (L.) and eggs of Bombyx mori (L.). Diapausing larvae of Ephestia elutella were highly tolerant, a few surviving to the adult stage after exposure to concentration-time (CT) products of up to 150 mg hr/l at 25°C and 260 mg hr/l at 15°C. Diapausing larvae of Plodia interpunctella were tolerant at low temperatures but quite susceptible at 25°C. In both species, larvae in diapause were four to six times more tolerant than other larvae at 15°C or below, and strains recently collected from the field were more tolerant than laboratory reared stocks.In E. elutella, differences in the method of induction, maintenance or termination of diapause did not affect tolerance to fumigation. P. interpunctella larvae reared at high population density were more susceptible than those reared at low density. Among strains of these species, a correlation was observed between the duration of larval diapause and tolerance to methyl bromide. Adults emerging after fumigation of diapausing larvae were of lowered fertility but rarely sterile. The CT products required for the complete control of moths in diapause were higher than those currently recommended for the disinfestation of stored products.Diapausing pupae of an outdoor species Pieris brassicae required the very high CT product of 403 mg hr/l for complete control at 25°C and were at least six times more tolerant than non-diapausing pupae. Diapausing eggs of Bombyx mori required 179 mg hr/l for complete control, while non-diapausing eggs were all killed by 125 mg hr/l.     

The tolerance of immature stages of four stored product moths to methyl bromide

Eggs, last instar larvae, and pupae of the Pyralid moths, Ephestia elutella (Hübner). E. kuehniella Zeller, E. cautella (Walker) and Plodia interpunctella (Hübner) reared at 25°C were exposed to methyl bromide over a wide range of concentrations and times at 10–30°C. One laboratory stock, and one field stock of each species were tested, but differences between stocks of the same species were small.P. interpunctella required lower CT products than the other species for complete kill of each stage. At 10°C, larvae of the field stock of E. cautella required a CT product of 110 mg h/l. for complete control. All stages of all species succumbed to a CT product of 64 mg h/l. at 15°C. When exposed at 20°C or above, pupae aged 0–3 days were more tolerant than other stages. Eggs aged 2 days or over were more tolerant than younger ones.The fertility of survivors from fumigated eggs resembled that of controls, but that of some individuals fumigated as pupae was depressed. For fumigated eggs of E. elutella and P. interpunctella at 15°C, the CT relationship held over concentrations from 4·2 to 10·8 mg/l. and exposure periods from 1 to 16 h.     

A review of the properties and usage of methyl bromide as a fumigant

The properties which make methyl bromide an effective fumigant and the range of commodities treated with it are reviewed. The problems associated with the various situations in which fumigations are carried out and the methods of application used are discussed, and consideration is given to the toxicity of methyl bromide to man and other mammals, and to the risks involved in its use. Analytical methods for determining methyl bromide in air and residual bromide in foodstuffs are reviewed and a Table of physical properties and other reference data is given as an Appendix.