Concentration-time relationships for methyl isothiocyanate in soil after injection of metham-sodium

Soil fumigation with metham-sodium in the field was studied in detail by characterising soil and climatic conditions, and by measuring concentrations of methyl isothiocyanate. The effectiveness of two dosages in two contrasting soil profiles was compared on the basis of computed concentration-time products for methyl isothiocyanate in the water phase. Under wet conditions, the vapour diffusion of methyl isothiocyanate was very slow and resulted in an irregular distribution in the soil. Showers further decreased effectiveness in the upper part of the soil. A dried top layer was unfavourable for the concentration-time product near to the surface. Diffusion of methyl isothiocyanate to depths greater than about 30 cm was very slow.     

实验室条件下威百亩及异硫氰酸甲酯在土壤中的降解特性

在实验室条件下,利用高效液相色谱研究了威百亩及其降解产物异硫氰酸甲酯在土壤中的降解特性及影响因素。结果表明:威百亩在土壤中的降解与土壤绝对含水量、环境温度和土壤有机质含量均密切相关。25 ℃下,威百亩在绝对含水量为0、20%、40%、60%的土壤中的半衰期分别为5.0、1.2、4.1和4.3 d,绝对含水量约为20%的土壤最有利于其降解。威百亩的降解速率还随温度的升高和土壤有机质含量的增加而加快。异硫氰酸甲酯的降解趋势与威百亩基本相同。研究结果可为威百亩的田间安全、合理施用提供参考。     

Surface water seal application to minimize volatilization loss of methyl isothiocyanate from soil columns

BACKGROUND: Metam‐sodium (MS, sodium methyldithiocarbamate) has been identified as a promising alternative chemical to replace methyl bromide (MeBr) in soil preplant fumigation. One degradation product of MS in soil is the volatile gas methyl isothiocyanate (MITC) which controls soilborne pests. Inconsistent results associated with MS usage indicate that there is a need to determine cultural practices that increase pest control efficacy. Sealing the soil surface with water after MS application may be a sound method to reduce volatilization loss of MITC from soils and increase the contact time necessary for MITC to control pests. The objective of this research was to develop a preliminary soil surface water application amount that would potentially inhibit the off‐gassing rate of MITC. RESULTS: Off‐gassing rate was consistently reduced with increasing water seal application. The application of a 2.5–3.8 cm water seal provided significantly lower (71–74% reduction in MITC volatilization) total fumigant loss compared with no water seal. The most favorable reduction in MITC off‐gassing was observed in the 2.5 cm water seal. CONCLUSION: This suggests that volatilization of MITC‐generating compounds can be highly suppressed using adequate surface irrigation following chemical application in this soil type (sandy clay loam), based on preliminary bench‐scale soil column studies. Copyright © 2010 Society of Chemical Industry     

药液稀释倍数对威百亩分解产生异硫氰酸甲酯及其消解的影响

种植前施用威百亩进行土壤熏蒸消毒, 其分解产生的异硫氰酸甲酯（methyl isothiocyanate, MITC）可有效控制土传病原菌。威百亩以滴灌方式施用更为方便、安全, 但在滴灌前的稀释过程中可能会水解产生MITC, MITC继续消解或挥发导致进入土壤的有效成分量减少。因此有必要筛选适宜的威百亩稀释倍数, 保证MITC在土壤中分布均匀的同时减少威百亩分解及MITC消解和挥发导致的损失。本文研究了不同pH条件下稀释倍数对威百亩水解产生MITC及MITC消解的影响。结果表明, 在中性条件下, 由威百亩水解产生的MITC量及其消解速率均随稀释倍数增加而增加;在酸性条件下, 稀释100倍时MITC的产生量及消解速率均为最大, 稀释50倍时MITC的产生量最低, 稀释400倍时MITC消解最慢;在碱性条件下, MITC的产生量随稀释倍数增加而增加, 消解速率为稀释1 000倍时最快, 稀释100倍时最慢。研究结果对滴灌施用威百亩时田间用水量及威百亩用量均具有指导意义。     

Distribution and efficacy of drip-applied metam-sodium against the survival of Rhizoctonia solani and yellow nutsedge in plastic-mulched sandy soil beds

The effects of metam-sodium application rate on soil residence time, spatial and temporal distributions of methyl isothiocyanate and pest control efficacy were studied in a Georgia sandy soil. Metam-sodium 420 g L(-1) SL was drip applied at rates of 147 and 295 L ha(-1) in plastic-mulched raised beds. Methyl isothiocyanate concentrations in soil air space were monitored from four preselected sites: 10 and 20 cm below the emitter, and 20 and 30 cm laterally away from the emitter at 3, 12, 24, 48, 72, 120 and 240 h after chemigation. A higher rate of metam-sodium application resulted in higher methyl isothiocyanate concentrations in the soil. Highest methyl isothiocyanate concentrations were found at 20 cm below the emitter, and lowest at 30 cm laterally away from the emitter. Methyl isothiocyanate concentrations decreased with time and distance from the emitter. Lower methyl isothiocyanate concentration x time product values at 20 and 30 cm away from the emitter resulted in lower mortalities of Rhizoctonia solani Kühn and yellow nutsedge (Cyperus esculentus L.). The results demonstrated that methyl isothiocyanate can be delivered at lethal doses with drip-applied water downward within the beds. Lateral diffusion of methyl isothiocyanate from the point of application did not reach biologically active concentrations to affect the survival of R. solani or yellow nutsedge. Further studies on the lateral distribution of methyl isothiocyanate in sandy soils are needed to circumvent this limitation.     

Evaluation of chemical and integrated strategies as alternatives to methyl bromide for the control of root-knot nematodes in Greece

Current environmental awareness has led to a greater demand for alternative nematode control strategies. Three field experiments were established to compare management tactics on cucumber in commercial greenhouses naturally infested with root-knot nematodes (Meloidogyne spp). Cucumber rootstocks which have shown resistance to soil-borne diseases were tested to reveal any resistance/tolerance to root-knot nematodes, and integration of these rootstocks with nematicides was investigated. Metham-sodium and 1,3-dichloropropene (1,3-D) provided good control of nematode populations when their application was followed by the application of a non-fumigant nematicide such as cadusafos or oxamyl. Neither fumigant could provide season-long control of nematode populations, and a further application of cadusafos was required for satisfactory control. The efficacy of metham-sodium was significantly increased when injected into soil in comparison with its application through the drip irrigation system. The use of rootstocks resistant to soil-borne fungal pathogens used together with chemical means of nematode control provided promising results for their further use in integrated strategies as alternatives to methyl bromide. However, the latter was the superior treatment for the control of root-knot nematodes in soil infested with residues of galled roots. Dazomet, metham-sodium nor the non-fumigant nematicides oxamyl and fenamiphos could reduce nematode population as efficiently as methyl bromide. None of the chemicals tested except methyl bromide could enter galled roots and kill surviving nematodes.     

Soil fumigation with dichloropropene and metham-sodium: Effect of soil cultivations on dose pattern

In field trials, loamy soils were fumigated by injecting dichloropropene and metham-sodium with a horizontal-blade injector. Concentrations of cis- and trans-1,3-dichloropropene, and of methyl isothiocyanate were measured. The influence of different methods of tillage on fumigation effectiveness was compared by computing concentration-time products at the various depths in the soil. With a fine-structured top layer, there was no clear beneficial effect of shallow or deep rotary tillage before injection. If a dense top layer was not rotary-tilled beforehand, deep and wide cracks were formed during injection. Shallow or deep rotary tillage both left loose cereal stubble mixed in the surface layer, which was difficult to finish off. Concentration-time products could be substantially increased by finishing off the soil surface better after injection.     

Chemical alternatives to methyl bromide for the control of root-knot nematodes in greenhouses

The complete phase-out of methyl bromide from use in developed countries by 1 January 2005 will cause many problems in agricultural industries that are now heavily reliant on its use. Three field experiments were established to compare management tactics on tomato and cucumber in commercial greenhouses naturally infested with root-knot nematodes (Meloidogyne spp). Reduction of nematode juveniles in soil and roots to nil detection levels was observed in all plots following soil fumigation with methyl bromide. A significant reduction of nematode juveniles and root-galling index was observed in plots treated with metham-sodium, dazomet and 1,3-dichloropropene compared with the control and plots treated with non-fumigant nematicides. Reduction of the nematode population led to an increase in fruit yield. However, data collected from the second cultivation season indicated that single control methods such as fumigant or contact nematicides alone cannot drastically decrease initial nematode population and those nematodes which escape control lead to population increase by the end of the cropping season.     

溴甲烷土壤消毒替代技术研究进展

概述了溴甲烷替代品的新进展。在土壤消毒方面,新的进展有化学替代品:氯化苦胶囊、氯化苦乳剂、氯化苦+噻唑磷混用、C₂N₂、氰铵化钙、异硫氰酸烯丙酯、异硫氰酸甲酯、1,3—二氯丙烯和氯化苦混剂、碘甲烷、环氧丙烷、叠氮化合物、硫酰氟等。在使用技术上,采用化学灌溉和注射施药技术进一步提高药剂分布的均匀性。在非化学替代技术上,生物熏蒸和有机质补充正受到重视。减少溴甲烷的技术正在快速地发展。     

Biofumigation: environmental impacts on the biological activity of diverse pure and plant-derived isothiocyanates

Four pure isothiocyanates (methyl, 2-propenyl, benzyl and 2-phenylethyl isothiocyanate), hydrolysing tissue of two brassicas rich in either 2-propenyl or 2-phenylethyl isothiocyanate, and the methyl isothiocyanate-generating pesticide metam-sodium were tested in vapour exposure tests for biological activity against a model soil insect both in vitro and in the presence of three contrasting soils and under four temperatures from 5 to 20 degrees C. The purpose was to develop an understanding of the factors controlling isothiocyanate release and maintenance in soil in order to identify advantageous attributes to seek in utilising brassicas for isothiocyanate-based biofumigation. Methyl isothiocyanate, structurally the simplest and the most volatile, was the most biologically active isothiocyanate under all conditions. It was less affected by the presence of soil and by lower temperature than the longer-chain aliphatic 2-propenyl isothiocyanate. The activity of the less volatile aromatic isothiocyanates was reduced much more by soil, with a decline up to many thousand-fold in the presence of soil with high organic matter content at lower temperature. Metam-sodium closely reflected the methyl isothiocyanate results. The results indicate that brassicas rich in aliphatic isothiocyanates are more likely to have the potential to exert stronger isothiocyanate-based biofumigation effects than those similarly rich in aromatic isothiocyanates.     

Effect of soil physical factors on methyl iodide and methyl bromide

Production and importation of methyl bromide is scheduled to be banned by 2001. Methyl iodide was evaluated as a possible replacement soil fumigant. The effects of soil moisture, temperature, soil texture and fumigation time on the efficacy of methyl iodide for the control of two common weeds, Abutilon theophrasti and Lolium multiflorum, were characterized and compared with those of methyl bromide. The optimal soil moisture for methyl iodide to kill both weed species in sandy soils was 14% water content (w/w). Greater efficacy was obtained when the temperature during fumigation was above 20°C. Compared to methyl bromide, the efficacy of methyl iodide was more consistent in different soils. Time to 100% mortality of weeds was 24 h for methyl iodide fumigation and 36 h for methyl bromide when 200 μM of fumigant was used. On a molar basis methyl iodide was consistently more effective than methyl bromide across the range of environmental factors tested. In terms of application technology and spectrum of activity, methyl bromide can be directly replaced by methyl iodide. © 1998 SCI     

Dissipation of metham-sodium from soil and its effect on the control of Orobanche aegyptiaca

The effect of metham-sodium on Orobanche aegyptiaca Pers. was tested in the laboratory and in soil columns. The laboratory experiment was carried out on O. aegyptiaca seeds placed in Petri dishes and germinated with GR₂₄, a synthetic strigol analogue. In soil columns, metham-sodium was applied by application of the chemical through the irrigation water to three different soils and its dissipation determined in three soil layers by gas chromatography, by a lettuce bio-assay to check the herbicide's phytotoxicity, and with a flax bioassay to check its effect on O. aegyptiaca. Results of the germination experiments showed an exponential decrease in O. aegyptiaca germination, parallel with the increase of metham-sodium concentration, with an average effective concentration (EC₅₀) of 18 mg L^?1. In a soil column, methylisothiocyanate (MIT, the metham active product) rapidly disappeared from the upper soil level (0–10 cm) within 24 h. Seven days after application only traces of MIT remained in all soil layers in all soils, except for the sandy Rehovot soil that contained low concentrations in the lower soil layer (20–30 cm). Flax bioassay confirmed the chemical analysis, showing that O. aegyptiaca tubercles developed only on plants grown in the upper soil layer of all three soils.     

Fumigant distribution in forest nursery soils under water seal and plastic film after application of dazomet, metam-sodium and chloropicrin

Adequate concentration, exposure time and distribution uniformity of activated fumigant gases are prerequisites for successful soil fumigation. Field experiments were conducted to evaluate gas phase distributions of methyl isothiocyanate (MITC) and chloropicrin (CP) in two forest-tree nurseries. Concentrations of MITC and CP in soil air were measured from replicated microplots that received dazomet, metam-sodium and CP. Half of the plots were covered with high-density polyethylene tarp immediately after fumigation; the other half were not covered but received daily sprinkler irrigation for 1 week to create and maintain a water seal. The magnitude of MITC concentrations was similar between nurseries for metam-sodium in both tarp and water seal treatments and for dazomet in the tarp treatment. Consistently greater MITC and CP concentrations were found in the upper 30 cm of soil in the tarped plots compared with the water-sealed plots. Despite potential environmental and economic benefits with the water seal method, tarp covers were more reliable for achieving and maintaining higher MITC and CP concentrations and less prone to variations due to irrigation/rain, soil bulk density and other environmental conditions.     

Physical, chemical and environmental properties of selected chemical alternatives for the pre-plant use of methyl bromide as soil fumigant

Production and use of methyl bromide, a soil fumigant, are being restricted because of this chemical's deleterious effects on stratospheric ozone concentrations. Several products, some of which are currently used as soil fumigants, are being considered as possible replacements for methyl bromide, alone and in various combinations. Among these, 1,3-dichloropropene, methyl isothiocyanate generators such as metam-sodium, and chloropicrin are currently registered, while others such as methyl iodide and sodium azide are at different stages of the registration process. This review examines physicochemical properties, environmental fate, and metabolism of the various potential methyl bromide replacement products.     

Status of chemical alternatives to methyl bromide for pre-plant fumigation of soil

ABSTRACT None of the chemical alternatives currently registered and available has the full spectrum of activity and versatility of methyl bromide as a pre-plant soil fumigant. Chloropicrin and 1,3-dichloropropene (Telone) can provide significant control of many plant pathogens in soil and growth stimulation in annual crops. These compounds, however, provide limited control of weeds or other residual plant materials in soil of concern in nursery production systems, and some perennial replant diseases. Methyl isothiocyanate generators such as metam sodium have broad biocidal activity in soil, but are more difficult to apply effectively. In most soil applications, the available alternatives are likely to be used in combinations, either as mixtures (e.g., 1,3-dichloropropene and chloropicrin) or sequentially (e.g., chloropicrin followed by metam sodium). They may also be supplemented with other more specific pesticides and cultural controls. Among the alternatives currently under active development but not yet available, methyl iodide and propargyl bromide probably have activity that most closely parallels that of methyl bromide in soil. However, all of the chemical alternatives to methyl bromide will be subject to continuing review and more regulation. Furthermore, we do not know the actual prospects for registration of the new fumigants currently under development and there is a risk that registered fumigants will not be available for large-scale use in soil indefinitely.     

Residual free methyl bromide in fumigated commodities

The extent to which methyl bromide was retained by fumigated material after treatment was followed in laboratory studies on a range of commodities exposed to the vapour at atmospheric pressure. Amounts of methyl bromide, recovered by solvent extraction and determined using gas-liquid chromatography, were related to the temperature, moisture content and manner of post-treatment storage. Immediately after exposure, the initial amount of free methyl bromide present was more dependent on the gas concentration used than on the time of exposure. Under the experimental conditions of exposure, the residual free methyl bromide in all commodities fumigated at 25°, except cocoa beans and groundnuts, fell to below 1 ppm within a few days when they were held at that temperature, whether spread in thin layers on trays or kept sealed in glass bottles. At lower temperatures, the rate of loss was slower, small amounts of methyl bromide being extracted from several commodities one month after treatment. The disappearance of fumigant from wheat and sultanas was more rapid from samples with higher moisture contents. A mathematical treatment of the data is presented, to assist in prediction of the behaviour of residual fumigant under storage conditions before processing. It is concluded that the risk of ingestion of harmful quantities of free methyl bromide by the consumer is small and that the occasions when relatively high residues might occur can be predicted.     

A simulation model for fate and transport of methyl bromide during fumigation in plastic‐mulched vegetable soil beds

A coupled water‐heat and chemical transport model was used to describe the fate and transport of methyl bromide fumigant in low‐density polyethylene plastic‐mulched soil beds used for vegetable production. Methyl bromide transport was described by convective‐dispersive processes including transformations through hydrolysis. Effects of non‐isothermal conditions on chemical transport were considered through inclusion of temperature effects on transport parameters. An energy‐balance approach was used to describe the plastic‐mulched boundary condition that controls the thermal regime within the soil bed. Simulations were made for variable water‐saturation regimes within the bed and for different depths of fumigant injection. Simulations for various scenarios revealed that large amounts (20–44% over a 7‐day period) of applied methyl bromide are lost from the un‐mulched furrows between the beds. Plastic mulching of the bed was found to be only partially effective (11–29% emission losses over a 7‐day period) in reducing atmospheric emissions. Deep injection of fumigant and saturating the soil with water both led to increased retention of methyl bromide within the soil and less emission to the atmosphere. However, deep injection was unfavorable for effective sterilization of the crop root zone. © 2000 Society of Chemical Industry     

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.     

Leaching of Methyl Isothiocyanate in Plainfield Sand Chemigated with Metam-Sodium

Soil column studies were undertaken to investigate the influence of soil water content and irrigation on leaching, distribution and persistence of methyl isothiocyanate (MITC) in a sandy soil chemigated with the soil fumigant metam-sodium. No leaching was obtained from columns at low water content (0·042 or 0·074 cm³ cm⁻³). However, 8·4 (±2·8), 34·2 (±7·4) and 119·4 (±8·3) μg of MITC leached from columns at 0·105, 0·137 and 0·168 cm³ cm⁻³ water content, respectively. Increased leaching resulted from sprinkler application of 25-mm of water to columns at 0·137 cm³ cm⁻³ water content. Leaching of MITC constituted only a small fraction of the amount applied even in the worst case. Methyl isothiocyanate persisted in soil for 15 days at 2°C in varying amounts under the different water regimes. Relatively high amounts of MITC residues (8–12 mg kg⁻¹ soil) were detected in the top 25-cm layer of all the soil columns. Degradation was the major pathway of dissipation for the chemical despite the soil water regime.     

Methyl isothiocyanate volatilization from fields treated with metam‐sodium

Emission of methyl isothiocyanate (MITC) from fields treated with metam‐sodium (sodium N‐methyldithiocarbamate) is a potential environmental and human safety hazard. Concentrations of MITC at three heights above four arable fields were measured following the application of metam‐sodium at a rate of 480 litre ha⁻¹ (166 kg AI ha⁻¹). Two of these fields were treated by injection into a center‐pivot irrigation system (chemigation), while in the other two fields the fumigant was applied through injection directly into the soil. Generally, higher MITC air concentrations were observed above chemigated than above injected fields. Maximum MITC air concentrations were 11.2 and 7.4 µg m⁻³ recorded 10 cm above ground 6–8 h following application and the minimum concentrations were 0.7 and 0.2 µg m⁻³ observed at 200 cm 30–35 h after application above chemigated and injected fields, respectively. The estimated MITC respiratory exposure a worker might encounter during the re‐entry period ranged between 1.37 and 0.03 mg day⁻¹ in chemigated fields and between 0.35 and 0.02 mg day⁻¹ in the injected fields. These results suggest that application of the fumigant through injection reduced MITC volatilization losses in comparison with the chemigation method, thus posing a relatively lower risk of exposure to MITC emissions. © 2000 Society of Chemical Industry