A kinetic model of fumigant sorption by grain using batch experimental data

BACKGROUND: Most fumigants are adsorbed by grain at differing rates depending on the fumigant or grain type. Sorption can reduce the concentrations of fumigation doses to sublethal levels before grain has been disinfested. A model to predict fumigant losses due to sorption in industrial scenarios is needed. RESULTS: This work reviews the kinetics of grain fumigant sorption and develops a new alternative model based upon key factors established from the literature and batch experimental results. The novel model accounts for linear mass transfer within the grain, irreversible 'binding' and linear partitioning of the fumigant to the grain. Model coefficients were estimated by minimizing the sum of squared residuals between model predictions and experimental data. The model was compared with other options including diffusion into spheres, and results for methyl bromide and phosphine are provided. CONCLUSION: The model describes the transient changes of fumigant concentrations in both the intergranular air and grain. It provides the capacity to predict fumigant concentrations throughout grain stacks for a wide range of scenarios of industrial importance.     

Improved efficacy of ethyl formate against stored grain insects by combination with carbon dioxide in a 'dynamic' application

Ethyl formate is being evaluated as a fumigant for stored grain as it is a potential alternative to the ozone-depleting fumigant methyl bromide and to phosphine, which is under pressure owing to the development of strong resistance in stored grain insects. However, use of ethyl formate faces significant challenges, such as poor penetration through grain, significant losses to grain sorption, high concentrations of fumigant required to control insects, and flammability risks, which have limited its further development. In this study it was found that the combination of carbon dioxide (5-20%) with ethyl formate significantly enhanced efficacy of the fumigant against external living stages of the rice weevil, Sitophilus oryzae (L.), the lesser grain borer, Rhyzopertha dominica F., and the flour beetle, Tribolium castaneum (Herbst). Dynamic application of ethyl formate and carbon dioxide mixture (100 mg litre-1 ethyl formate, 20% CO2) pumped through a model silo containing wheat (50 kg) for one gas exchange was also investigated. A flow rate of 6 litres min-1 gave a relatively even distribution of fumigant throughout the grain column and similar mortality levels among cultures of S. oryzae and T. castaneum placed at three positions, the top, middle and bottom of the column. Mortality of 99.8% of mixed stage cultures of T. castaneum and 95.1% of S. oryzae was achieved in 3 h exposures to 111 and 185 mg ethyl formate h litre-1 respectively applied by the dynamic method. It is concluded that the combination of carbon dioxide with ethyl formate and dynamic application enhances distribution and efficacy of the fumigant against stored grain insects.     

Ethyl formate,formic acid and ethanol in air,wheat, barley and sultanas: analysis of natural levels and fumigant residues

Ethyl formate and ethanol in air, eg in fumigant studies, were readily detected by gas chromatography (GC) (flame ionisation). Residues in wheat, barley and sultanas were analysed by GC, after extraction in polar solvents (eg methanol, aqueous propanol). Both natural levels and levels resulting from fumigation with ethyl formate were measured. Formic acid was extracted from commodities with polar solvents (eg methanol, water) and analysed by GC after esterification. Solvent extracts of commodities were concentrated after addition of disodium hydrogen orthophosphate, and an aliquot added to acidified alcohols (several combinations of acids and alcohols were tested) in a sealed container. Formic acid esters were determined by GC, from headspace sampling over the esterification solvent. Esterification was faster with strong acids than with boric acid. However, esterification with boric acid/butanol gave the least interference of all tested methods. Product identity was confirmed by GC/mass spectrometry. High natural levels of formic acid, and low natural levels of ethyl formate and ethanol, presented problems in identifying residues arising from fumigation. These natural levels are relevant to food regulations for ethyl formate, especially those based on ‘total formic acid, free and combined’. Polar columns (eg FFAP, carbowax) were useful for measurement of formic acid esters, which eluted before the alcohols used for esterification or extraction, whereas elution followed the molecular mass on non-polar columns, such as GS-Q or DB-624. © 1999 Society of Chemical Industry     

Field evaluation of vaporised ethyl formate and carbon dioxide for fumigation of stored wheat

BACKGROUND: Vapormate? is a cylinderised non‐flammable mixture of ethyl formate (16.7% by weight) and carbon dioxide (CO₂) that has been developed as a rapid fumigant of stored grain. Four field trials were undertaken on wheat in 50 t farm silos to demonstrate the feasibility of dynamic application. To assess treatment efficacy, each trial tested mixed stages of Rhyzopertha dominica F. (>11 000), Tribolium castaneum (Herbst.) (>1500) and Sitophilus oryzae (L.) (>13 000) in mesh cages positioned through the centre of the grain bulk and on the grain surface. Ethyl formate and CO₂ concentrations were measured in the silo during fumigation and in ambient air outside the 6 m fumigation zone. Application rates of 420, 660 and 940 g m^?3 of ethyl formate/CO₂ formulation and exposure times of 24, 3 and 72 h, respectively, were examined using wheat of 10.4–11.7% moisture content and grain temperatures between 2 and 32 °C. RESULTS: All life stages of R. dominica and T. castaneum were fully controlled under all conditions tested, and mortality of all life stages of S. oryzae was greater than 98%. CONCLUSION: Dynamic application of vaporised ethyl formate and CO₂ to 50 t silos proved safe to operators and rapidly effective against stored‐grain insects on cold to warm grain. Copyright © 2009 CSIRO, Australia. Published by John Wiley & Sons, Ltd     

Ethyl formate plus methyl isothiocyanate--a potential liquid fumigant for stored grains

BACKGROUND: Methyl bromide is being phased out for use on stored commodities, as it is listed as an ozone‐depleting substance, and phosphine is the fumigant widely used on grains. However, phosphine resistance occurs worldwide, and phosphine fumigation requires a long exposure period and temperatures of > 15 °C. There is an urgent requirement for the development of a fumigant that kills insects quickly and for phosphine resistance management. This paper reports on a new fumigant formulation of 95% ethyl formate plus 5% methyl isothiocyanate as an alternative fumigant for stored grains. RESULTS: The formulation is stable for at least 4 months of storage at 45 °C. A laboratory bioassay with the formulation showed that it controlled all stages of Sitophilus oryzae (L.), Sitophilus granarius (L.), Tribolium castaneum (Herbst), Rhyzopertha dominica (F.), Trogoderma variabile Ballion and Callosobruchus maculatus (Fabricius) in infested wheat, barley, oats and peas at 80 mg L^?1 for 5 days, and in canola at both 40 mg L^?1 for 5 days and 80 mg L^?1 for 2 days at 25 ± 2 °C. After an 8–14 day holding period, residues of ethyl formate and methyl isothiocyanate in wheat, barley, peas and canola were below the experimental permit levels of 1.0 and 0.1 mg kg^?1. However, fumigated oats needed an 18 day holding period. CONCLUSIONS: The findings suggest that the ethyl formate plus methyl isothiocyanate formulation has potential as a fumigant for the control of stored‐grain insect pests in various commodities. Copyright © 2011 Society of Chemical Industry     

Efficacy of vaporised ethyl formate/carbon dioxide formulation against stored‐grain insects: effect of fumigant concentration,exposure time and two grain temperatures

BACKGROUND: The ethyl formate/carbon dioxide (CO₂) formulation Vapormate? is a rapid‐acting fumigant being developed for the control of stored‐grain insects. The effects have been investigated of concentration, exposure times of 1, 3, 24 and 72 h and two grain temperatures, 15 and 25 °C, on its efficacy against mixed‐stage cultures of Sitophilus oryzae (L.) Tribolium castaneum (Herbst) and strongly phosphine‐resistant Rhyzopertha dominica (F.) strain QRD569. RESULTS: High mortalities (≥92%) of mixed‐stage cultures of all three species were obtained when grain was fumigated with the formulation (193 g m^?3 ethyl formate) for 1 h. Complete control of R. dominica QRD569 and T. castaneum was achieved with 63 and 76 g m^?3 ethyl formate respectively, with exposure for 24 h, whereas mean mortality of S. oryzae was 86% under the same conditions. Mortalities of S. oryzae juvenile stages were significantly lower than adults under the conditions tested, which was due to pronounced tolerance of mid‐stage pupae to the fumigant. Reducing grain temperature from 25 to 15 °C had no effect on insect mortality. CONCLUSION: Ethyl formate/CO₂ formulation is highly effective against stored‐grain insects over a range of concentrations and exposure times. Efficacious fumigations were conducted in as little as 1 h, and a strongly phosphine‐resistant R. dominica strain was readily controlled with the fumigant. Copyright © 2009 CSIRO, Australia. Published by John Wiley & Sons, Ltd     

Sorption of sulfuryl fluoride by food commodities

BACKGROUND: The use of sulfuryl fluoride, a structural fumigant for termite and woodborer control, has recently been expanded to treating stored food commodities and food facilities. There is, however, a lack of data on the sorption of sulfuryl fluoride by food commodities. Knowledge about sorption is important in the context of effective treatment and residues.RESULTS: When sulfuryl fluoride was applied at a dose of 50 g m(-3) to various food commodities (total 68) with 300 g per replicate in 0.75 L gas wash bottles (fumigation chambers) at 25 +/- 1 degrees C, in most cases (81%) the gas concentrations in the free space of the commodities exceeded 50 g m(-3) (range 51-80 g m(-3)) at the end of 24 h exposure. In chambers without the substrate, an average concentration of 49.7 g m(-3) was recorded. About 54% of the commodities showed low-level ( < or = 25%) sorption of sulfuryl fluoride, 34% showed medium-level (26-50%) sorption and only 12% were highly sorptive (>50%). The latter include white oats (terminal gas concentration 17.8 g m(-3)), some of the decorticated split pulses (24.0-29.3 g m(-3)), chickpea flour (26.3 g m(-3)), dried ginger (29.0 g m(-3)), refined wheat flour (30.3 g m(-3)) and coriander powder (40.5 g m(-3)). In unfumigated control commodities, owing to interfering volatiles, Fumiscope readings in the range 0-13 were noted.CONCLUSION: Sulfuryl fluoride has the advantage of a low or moderate level of sorption with the majority of the food commodities.     

Fumigation toxicity of volatile natural and synthetic cyanohydrins to stored-product pests and activity as soil fumigants

Insecticidal fumigation toxicity of natural and synthetic cyanohydrins was evaluated with four stored-product pests: the lesser grain borer, Rhyzopertha dominica (F), the red flour beetle, Tribolium castaneum Herbst, the saw-toothed grain beetle Oryzaephilus surinamensis L, the maize weevil, Sitophilus zeamais (Motsch) and the house fly, Musca domestica L. The fumigation LC50 values were calculated by probit analysis. For house flies, all but one of the cyanohydrins tested were more potent than 1,3-dichloropropene (Telone). Three were as efficacious as chloropicrin. For the lesser grain borer, all cyanohydrins tested were more insecticidal than dichloropropene, and all but one were more potent than chloropicrin. Four were as insecticidal as dichlorvos. The acetate of 1-cyano-1-hydroxy-2-propene (CHP-ace) was also tested in soil for antifungal and antibacterial activity, and inhibition of weed seed germination. CHP-ace reduced the total soil bacterial and fungal counts significantly, and was effective in inhibiting the germination of weed seeds in soil, indicating a broad spectrum of activity as a soil fumigant.     

New techniques in fumigation under development by DEGESCH1

The diminishing availability of fumigant compounds makes it essential to improve fumigation techniques if adequate pest control is to be maintained. Three approaches developed by DEGESCH are discussed. Phosphine fumigation is now possible in cold weather if magnesium phosphide rather than aluminium phosphide is used as the source. Gas recirculation (the J-system) provides for much more rapid fumigation in large grain silos. Finally, techniques are being developed to allow material to be added to, or removed from, a store during fumigation without hazard to the applicator.     

Comparisons of simulated with measured transport and transformation of methyl bromide gas in soils

A simulation model is described for the transport of the fumigant, methyl bromide gas, away from injection chisels within the field. The injected methyl bromide is assumed to form cylindrical, parallel sources at the depth of injection. Transport of the methyl bromide is described by radial diffusion from the injection cylinders. The dissolution-distillation of methyl bromide gas in the soil water and on soil particles is accounted for by a first-order reversible kinetic equation or by an equilibrium relationship. The hydrolysis of methyl bromide gas to bromide anion is considered to occur according to a first-order irreversible equation. The model considers cases where the soil surface is and is not covered with an impermeable barrier to the diffusion of the gas. Simulated methyl bromide concentrations in the soil air, and bromide concentrations in the soil, compared reasonably well with measured values from several field sites. Comparison of the results of calculations, with and without plastic barriers at the soil surface, with experimental data, indicate that plastic barriers are ineffective in preventing diffusion of gas from the soil to the atmosphere. Calculations of mass balances show that as much as 70% of the applied methyl bromide had escaped to the atmosphere by 14 days after fumigation.     

我国土壤熏蒸消毒60年回顾

熏蒸剂棉隆和氯化苦于20世纪60年代在我国曾用于棉花黄萎病的防治,由于缺乏施药机械、相关施药标准和方法,加之与国外交流甚少,虽然发现熏蒸剂对土传病害有一定的效果,但一直未形成规模化应用。我国大量使用熏蒸剂进行土壤消毒处理始于20世纪90年代,随着溴甲烷的引进与广泛应用,溴甲烷的替代技术及产品研发,开启了我国土壤熏蒸消毒的新纪元。伴随着土壤消毒技术与理论的不断丰富,新型配套机械装备的成功研发,社会化服务模式的广泛运用,土壤熏蒸消毒在我国进入快速发展时期,大批专业化服务组织应运而生,为我国农作物病虫害的绿色防控、实施乡村振兴战略提供了强有力的技术支撑。该文从土壤熏蒸剂的种类、发展历史、基础理论的建立与阐明3方面综述了我国土壤熏蒸发展情况,并对我国土壤熏蒸消毒未来发展方向提出了展望。     

Use of heat for disinfestation and control of insects in dates: Laboratory and field trials

Heat treatment of dates at the time of harvest, was examined as an alternative to fumigation with methyl bromide, which has been phased out in Israel under the Montreal Protocol. In laboratory studies, the influence of 40°, 45°, 50° and 55°C on the levels of disinfestation and mortality ofCarpophilus hemipterus larvae was examined over a 2-h exposure period. The ratio of the number of insects found outside the feeding sites to the total number of insects, was greatest at 50°C (92.3%), significantly greater than at 40° and 55°C. At 50° and 55°C, 100% mortality was obtained. Since drying temperatures for most date varieties is between 45° and 50°C, and because percent disinfestation and control was most effective at 50°C, these findings were examined under field conditions. Field trials were carried out at a commercial drying station where the crated dates are placed on the ground inside a plastic-clad hothouse. The stacks were covered with plastic liners to form ‘drying ducts’ through which heated air was sucked using fans positioned at the opposite end of the ducts. It was shown that from 1 to 2 h were required for the dates to reach the set temperature of 50°C. During the following 2-h aeration, the dates were exposed to 50°C heated air, after which an examination of infested dates inserted into the drying ducts, and natural infestations showed that successful control and emigration were obtained. This method produced results comparable to those obtained with methyl bromide fumigation, and was suitable as a replacement technology for infestation control. http://www.phytoparasitica.org posting Nov. 7, 2005.     

Permeation of soil fumigants through agricultural plastic films

Plastic films are used in soil fumigation to control fumigant emission into the atmosphere. In previous studies it was shown that the plastic films are permeable to fumigant vapors. Virtually impermeable films (VIF) have been developed to reduce such emission and to increase the efficacy of pest control. A rapid, accurate, sensitive and simple method to measure the permeability of plastic films to soil fumigants that was developed in the present study is described in this paper. The method uses a static, closed system in which the tested film is fixed between two cells. The fumigant is sampled by a solid-phase microextraction method and measured quantitatively by gas chromatography. The method was used to assess the permeability of two plastic films — a low-density polyethylene film (LDPE) and a VIF — to commercial soil fumigants formulated individually or in mixtures. All the tested fumigants permeated through the commonly used LDPE film, in the following descending order of permeability: methyl isothiocyanate (MITC), methyl bromide (MBr), 1,3-dichloropropene (1,3-D; Telone), chloropicrin (CP). The VIF was impermeable to all the tested fumigants except MITC, the permeation of which was reduced by 40%. The permeation of some fumigants through LDPE films was influenced by the formulation used. The permeation of CP was increased when it was combined with MBr in Bromopic. With Telopic, a mixture of 1,3-D and CP, the permeation of 1,3-D through LDPE film was 62% greater than that of Telone, whereas that of CP was not affected. The permeation rates of both MBr and CP were 25–30% greater when they were formulated as a mixture in Bromopic than when they were formulated individually. The formulation of fumigants as mixtures of two components did not affect their permeability through VIF. This study showed that differences in the suitability of plastic films for soil fumigation can be measured easily in a laboratory. It also showed that the VIP was more effective than LDPE in reducing losses of fumigant to the atmosphere, thus allowing more efficient use of fumigants to manage soilborne pests. The presented method helps us to choose the most adequate film for optimizing fumigation efficacy, and reducing costs and environmental risks. http://www.phytoparasitica.org posting Sept. 17, 2006.     

甲酸乙酯对面粉中赤拟谷盗的熏蒸效果

本文研究了甲酸乙酯对面粉中赤拟谷盗不同虫态的熏蒸作用。通过对熏蒸期间熏蒸剂浓度检测,计算浓度时间乘积(CT)计算不同时间下甲酸乙酯对赤拟谷盗各虫态达到99%控制的处理指标(Lct_(99))。结果表明甲酸乙酯熏蒸能有效防治面粉中的赤拟谷盗各虫态,赤拟谷盗不同虫态对甲酸乙酯的敏感性由强到弱依次为:卵>低龄幼虫>成虫>高龄幼虫>蛹。在23℃条件下处理6h和12h对面粉中赤拟谷盗的Lct_(99)分别为448.42和599.34mg·h/L     

甲酸乙酯对米象乙酰胆碱酯酶和羧酸酯酶的影响

报道了甲酸乙酯对米象[Sitophilus oryzae(Linnaeus)]乙酰胆碱酯酶(AChE)和羧酸酯酶(CarE)的活性影响,甲酸乙酯对米象表现出很高的毒力,25℃下熏蒸处理24 h的LC₅₀为28.65μL/L。亚致死剂量的甲酸乙酯可以使米象成虫体内AChE的比活力显著下降,用20μL/L的浓度处理24 h,AChE的比活力由15.684 nmol/mg.min下降至9.530 nmol/mg.min;酶动力学研究表明,甲酸乙酯可使米象成虫体内AChE的K_m值明显增加。对于羧酸酯酶,在活体条件下表现为先抑制后激活的规律,离体条件下则主要表现为抑制作用,且随着药剂浓度的增大抑制率也增大。     

Effect of phosphine dose on sorption in wheat

BACKGROUND: In spite of the extensive use of phosphine fumigation around the world to control insects in stored grain, and the knowledge that grain sorbs phosphine, the effect of concentration on sorption has not been quantified. A laboratory study was undertaken, therefore, to investigate the effect of phosphine dose on sorption in wheat. Wheat was added to glass flasks to achieve filling ratios of 0.25-0.95, and the flasks were sealed and injected with phosphine at 0.1-1.5 mg L(-1) based on flask volume. Phosphine concentration was monitored for 8 days at 25 degrees C and 55% RH. RESULTS: When sorption occurred, phosphine concentration declined with time and was approximately first order, i.e. the data fitted an exponential decay equation. Percentage sorption per day was directly proportional to filling ratio, and was negatively correlated with dose for any given filling ratio. Based on the results, a tenfold increase in dose would result in a halving of the sorption constant and the percentage daily loss. Wheat was less sorptive if it was fumigated for a second time. CONCLUSIONS: The results have implications for the use of phosphine for control of insects in stored wheat. This study shows that dose is a factor that must be considered when trying to understand the impact of sorption on phosphine concentration, and that there appears to be a limit to the capacity of wheat to sorb phosphine.     

Behaviour of the insecticides ethoprophos and carbofuran during soil—water transport

The movement of the organophosphate nematicide-insecticide ethoprophos (ethoprop; O-ethyl S,S-dipropyl phosphorodithioate) and the carbamate insecticide-nematicide carbofuran (2,3-dihydro-2,2-dimethylbenzofuran-7-yI methylcarbamate) was studied under steady-state flow in small-scale laboratory soil columns. Miscible displacement column experiments, mass balance calculations, and batch incubation studies furnished information on insecticide sorption and degradation processes that occur during transport through soil. Miscible displacement studies demonstrated that ethoprophos degradation could be described as first-order and that both insecticides exhibited non-equilibrium sorption. Both batch and miscible displacement results showed ethoprophos to be more strongly sorbed by soil than carbofuran. Measured equilibrium sorption coefficients were 1.29 cm³ g^?1 for ethoprophos and 0.29 cm³ g^?1 for carbofuran on a Riverhead soil (0.011 organic carbon fraction); 035 cm³ g^?1 for carbofuran on Valois soil (0.016 organic carbon fraction); and 2.38 cm³ g^?1 for ethoprophos on Rhinebeck soil (0.031 organic carbon fraction). Two solutions to the convection-dispersion equation, one that incorporated equilibrium sorption and another (bicontinuum model) that included a non-equilibrium sorption term, allowed quantitative evaluation of transport processes. The bicontinuum model used in conjunction with experimental batch and mass balance techniques provided estimates of insecticide sorption and degradation parameters.     

Formic acid: A neurologically active, hydrolyzed metabolite of insecticidal formate esters

Formate esters have potential uses as insecticides in both grain fumigation and public health pest management. This research investigated the hydrolytic metabolism and neurological effects of formate ester compounds. Studies were conducted using Drosophila and houseflies as models for other dipteran pests of medical importance. Results indicated significant formic acid liberation from a broad range of formate esters, both in vivo and in vitro. Based on these initial observations, we subsequently investigated neurological effects of formic acid on the larval housefly nervous system. We found that formic acid caused significant neuroexcitation at concentrations lower than previously shown for inhibition of insect cytochrome c oxidase; however, this conclusion does not preclude that mitochondrial effects may also be occurring in non-nervous tissues. Finally, we investigated formate ester hydrolysis by A- and B-type esterases commonly considered in pesticide detoxification research; however, no significant interactions could be identified, suggesting that as yet unidentified carboxylesterases play roles in formate ester hydrolysis. These findings provide information on formate ester metabolism and modes of action, as well as rationale for further studies on formate ester neurotoxicology and mechanisms of selective toxicity.