Comparisons of soil surface sealing methods to reduce fumigant emission loss

State and federal regulatory agencies depend on quality field data for determining the effects of agricultural management practices on fumigant emissions to develop sound, science-based policies and regulations on preplant soil fumigants. Field plot tests, using growers' standard field operation procedures, were used to simultaneously determine the effectiveness of several commonly proposed emission reduction methods, in a trial involving shank injection of Telone II [a.i. 1,3-dichloropropnene (1,3-D)] to a sandy loam soil to a target rate of 372 kg ha(-1). The experiment was conducted in late September 2008 in the San Joaquin Valley of California. Fumigant emissions were captured using dynamic flux chambers. The results showed that virtually impermeable film (VIF) reduced emissions >95% when compared to bare soil, and the glue joints in the film did not significantly affect the tarp performance. The VIF also created a more uniform distribution of gaseous fumigant in the soil profile, which would likely benefit pest control efficacy. Standard high-density polyethylene (HDPE) tarp reduced total 1,3-D emissions about 50% (higher than most reported values) in this trial, whereas postfumigation intermittent water treatments (seals) reduced cumulative emission losses by approximately 20%. Adding 49.4 Mg ha (equivalent to 20 tons per acre) of composted dairy manure to surface soils did not reduce 1,3-D emissions during this experiment. Use of VIF was the most promising technique in reducing emissions and has the potential to allow lower application rates while providing satisfactory pest control.     

Surface seals reduce 1,3-dichloropropene and chloropicrin emissions in field tests

Reducing emissions is essential for minimizing the impact of soil fumigation on the environment. Water application to the soil surface (or water seal) has been demonstrated to reduce 1,3-dichloropropene (1,3-D) emissions in soil column tests. This study determined the effectiveness of water application to reduce emissions of 1,3-D and chloropicrin (CP) in comparison to other surface seals under field conditions. In a small-plot field trial on a Hanford sandy loam soil (coarse-loamy, mixed, superactive, nonacid, thermic Typic Xerorthents) in the San Joaquin Valley, CA. Telone C35 (61% 1,3-D and 35% CP) was shank-applied at a depth of 46 cm at a rate of 610 kg ha-1. Soil surface seal treatments included control (no tarp and no water application), standard high density polyethylene (HDPE) tarp over dry and pre-irrigated soil, virtually impermeable film (VIF) tarp, initial water application by sprinklers immediately following fumigation, and intermittent water applications after fumigation. The atmospheric emissions and gas-phase distribution of fumigants in soil profile were monitored for 9 d. Among the surface seals, VIF and HDPE tarp over dry soil resulted in the lowest and the highest total emission losses, respectively. Intermittent water applications reduced 1,3-D and CP emissions significantly more than HDPE tarp alone. The initial water application also reduced emission peak and delayed emission time. Pre-irrigated soil plus HDPE tarp reduced fumigant emissions similarly as the intermittent water applications and also yielded the highest surface soil temperature, which may improve overall soil pest control.     

Evaluation of fumigation and surface seal methods on fumigant emissions in an orchard replant field

Soil fumigation is an important management practice for controlling soil pests and enabling successful replanting of orchards. Reducing emissions is required to minimize the possible worker and bystander risk and the contribution of fumigants to the atmosphere as volatile organic compounds that lead to the formation of ground-level ozone. A field trial was conducted in a peach orchard replant field to investigate the effects of fumigation method (shank-injection vs. subsurface drip-application treatments) and surface treatments (water applications and plastic tarps) on emissions of 1,3-dichloropropene (1,3-D) and chloropicrin (CP) from shank-injection of Telone C-35 and drip application of InLine. Treatments included control (no water or soil surface treatment); standard high-density polyethylene (HDPE) tarp, virtually impermeable film (VIF) tarp, and pre-irrigation, all over shank injection; and HDPE tarp over and irrigation with micro-sprinklers before and after the drip application. The highest 1,3-D and CP emission losses over a 2-wk monitoring period were from the control (36% 1,3-D and 30% CP) and HDPE tarp (43% 1,3-D and 17% CP) over shank injection. The pre-irrigation 4 d before fumigation and VIF tarp over shank injection had similar total emission losses (19% 1,3-D and 8-9% CP). The HDPE tarp and irrigations over subsurface drip-application treatments resulted in similar and the lowest emission losses (12-13% 1,3-D, and 2-3% CP). Lower fumigant concentrations in the soil-gas phase were observed with drip-application than in the shank-injection treatments; however, all treatments provided 100% kill to citrus nematodes in bags buried from 30 to 90 cm depth. Pre-irrigation and drip application seem to be effective to minimize emissions of 1,3-D and CP.     

Using surface water application to reduce 1,3-dichloropropene emission from soil fumigation

High emissions from soil fumigants increase the risk of detrimental impact on workers, bystanders, and the environment, and jeopardize future availability of fumigants. Efficient and cost-effective approaches to minimize emissions are needed. This study evaluated the potential of surface water application (or water seal) to reduce 1,3-dichloropropene (1,3-D) emissions from soil (Hanford sandy loam) columns. Treatments included dry soil (control), initial water application (8 mm of water just before fumigant application), initial plus a second water application (2.6 mm) at 12 h, initial plus two water applications (2.6 mm each time) at 12 and 24 h, standard high density polyethylene (HDPE) tarp, initial water application plus HDPE tarp, and virtually impermeable film (VIF) tarp. Emissions from the soil surface and distribution of 1,3-D in the soil-gas phase were monitored for 2 wk. Each water application abruptly reduced 1,3-D emission flux, which rebounded over a few hours. Peak emission rates were substantially reduced, but total emission reduction was small. Total fumigant emission was 51% of applied for the control, 46% for initial water application only, and 41% for the three intermittent water applications with the remaining water treatment intermediate. The HDPE tarp alone resulted in 45% emission, while initial water application plus HDPE tarp resulted in 38% emission. The most effective soil surface treatment was VIF tarp (10% emission). Surface water application can be as effective, and less expensive than, standard HDPE tarp. Frequent water application is required to substantially reduce emissions.     

Competitive degradation between the fumigants chloropicrin and 1,3-dichloropropene in unamended and amended soils

The mixture of 1,3-dichloropropene (1,3-D) and chloropicrin (CP) is used as a preplant soil fumigant. In comparison with individual fumigants, application of a mixture may affect the environmental dissipation and fate of each chemical, such as emission and degradation. We investigated the degradation of CP, 1,3-D, and their mixture in fresh soils and sterile soils, and evaluated the competitive characteristic of fumigants in the mixture. The degradation of low concentrations of CP in fresh soil was accelerated at early times in the presence of 1,3-D, whereas the addition of CP reduced the degradation rate of trans-1,3-D, possibly by inhibiting the activity of trans-1,3-D degrading microorganisms. The potential of applying amendments to the soil to increase the rate of CP and 1,3-D degradation was also illustrated. The degradation of both fumigants was significantly enhanced in soils amended with ammonium thiosulfate (ATS) and sodium diethyldithiocarbamate (Na-DEDTC) compared with unamended soil. Competitive degradation was observed for CP in amended soils in the presence of 1,3-D. The degradation of cis-1,3-D in amended soils spiked as a mixture of 1,3-D and CP was repressed compared with the rate of degradation in samples spiked with 1,3-D only. This implied that in abiotic degradation, CP and cis-1,3-D competed for a limited number of reaction sites in amended soil, resulting in decreased degradation rates. No significant influence of fumigant mixtures was observed for trans-1,3-D in amended soil.     

Lateral movement of soil fumigants 1,3-dichloropropene and chloropicrin from treated agricultural fields

The soil fumigants 1,3-dichloropropene (1,3-D) and chloropicrin (CP) are often used for controlling soil-borne plant pathogens and parasitic nematodes before reestablishing new vineyards and orchards. To evaluate crop safety and environmental risks with the replant fumigation, four field experiments were performed over 2 yr to examine 1,3-D and CP lateral movement away from the treated fields. Shank injection with or without a virtually impermeable film (V1F) was used in two vineyard fumigation experiments, and spot drip application without tarp cover was used in two orchard experiments. Results showed that 1,3-D and CP gases moved laterally to 6 m from the treated fields when the fumigants were applied by shank injection. The maximum 1,3-D or CP soil gas concentration at 6 m was approximately 10 ng cm(-3) when the fumigated plot was not cover with a tarp. With VIF, the measured maximum concentration increased to approximately 100 ng cm(-3). In the spot drip application, maximum 1,3-D and CP gas concentrations reached approximately 100 ng cm(-3) but at 1.5 m radial distance from the point of fumigant injection.     

Chloropicrin emissions after shank injection: two-dimensional analytical and numerical model simulations of different source methods and field measurements

Understanding the control mechanisms of fumigant movement in soil is a fundamental step for developing management strategies to reduce atmospheric emissions. Most soil fumigants including chloropicrin (CP) are applied by shank injection, and the application process often leaves vertical soil fractures that would potentially cause preferential fumigant movement and increased emissions. This potential transport pathway was evaluated by comparing cumulative emissions and soil air concentrations of CP from direct field measurements with those predicted using analytical and numerical models after assuming either point or rectangle sources for the injected CP. Results clearly showed that shank-injected CP, when treated as vertical rectangle sources, produced cumulative emission losses similar to the field measurements. Treating the shanked CP as point sources caused approximately 50% underprediction than the field measurements. The study also demonstrated that fumigant cumulative emissions can be predicted, with reasonable accuracy, using either analytical or numerical simulations.     

Soil fate of agricultural fumigants in raised-bed, plasticulture systems in the southeastern United States

Soil concentrations and degradation rates of methyl isothio-cyanate (MITC), chloropicrin (CP), 1,3-dichloropropene (1,3-D), and dimethyl disulfide (DMDS) were determined under fumigant application scenarios representative of commercial raised bed, plastic mulched vegetable production systems. Five days after application, 1,3-D, MITC, and CP were detected at concentrations up to 3.52, 0.72, and 2.45 μg cm, respectively, in the soil atmosphere when applications were made in uniformly compacted soils with a water content >200% of field capacity and covered by a virtually impermeable or metalized film. By contrast, DMDS, MITC, and CP concentrations in the soil atmosphere were 0.81, 0.02, and 0.05 μg cm, respectively, 5 d after application in soil containing undecomposed plant residue, numerous large (>3 mm) clods, and water content below field capacity and covered by low-density polyethylene. Ranked in order of impact on the persistence of fumigants in soil were soil water content (moisture), soil tilth (the physical condition of soil as related to its fitness as a planting bed), the type of plastic film used to cover fumigated beds, and soil texture. Fumigants were readily detected 13 d after application when applied in uniformly compacted soils with water contents >200% of capacity and covered by a virtually impermeable or metalized film. By contrast, 1,3-D and MITC had dissipated 5 d after application in soils with numerous large (>3 mm) clods and water contents below field capacity that were covered by low-density polyethylene. Soil degradation of CP, DMDS, and MITC were primarily attributed to biological mechanisms, whereas degradation of 1,3-D was attributed principally to abiotic factors. This study demonstrates improved soil retention of agricultural fumigants in application scenarios representative of good agricultural practices.     

Measuring flux of soil fumigants using the aerodynamic and dynamic flux chamber methods

Methods for measuring and estimating flux density of soil fumigants under field conditions are important for the purpose of providing inputs to air dispersion models and for comparing the effects of management practices on emission reduction. The objective of this study was to measure the flux of 1,3-dichloropropene (1,3-D) and chloropicrin at a site in Georgia (GA) using the aerodynamic method and the dynamic flux chamber (FC) method. A secondary objective was to compare the effects of high density polyethylene (HDPE), and virtually impermeable film (VIF) tarps on fumigant flux at a site in Florida (FL). Chloropicrin and 1,3-D were applied by surface drip application of In-Line soil fumigant on vegetable beds covered by low density polyethylene (LDPE), HDPE, or VIF. The surface drip fumigation using In-Line and LDPE tarp employed in this study resulted in volatilization of 26.5% of applied 1,3-D and 11.2% of the applied chloropicrin at the GA site, as determined using the aerodynamic method. Estimates of mass loss obtained from dynamic FCs were 23.6% for 1,3-D and 18.0% for chloropicrin at the GA site. Flux chamber trials at the FL site indicate significant additional reduction in flux density, and cumulative mass loss when VIF tarp is used. This study supports the use of dynamic FCs as a valuable tool for estimating gas flux density from agricultural soils, and evaluating best management practices for reducing fumigant emissions to the atmosphere.     

Use of SOFEA to predict 1,3-D concentrations in air in high-use regions of California

Methyl bromide, a commonly used soil fumigant, is being phased out per the Montreal Protocol and multiple fumigants are being positioned as replacements. Most effective soil fumigants, including methyl bromide, have the potential for inhalation exposure if the material volatilizes from soil. Chronic exposures for the fumigant 1,3-dichloropropene (1,3-D) are managed in part by the California Department of Pesticide Regulation by limiting the annual amount that can be used within a given township. A stochastic/deterministic numerical system (SOil Fumigant Exposure Assessment system [SOFEA]) was developed using the USEPA air dispersion model ISCST3, field study observations for flux loss, and links to Geographic Information Systems (GIS). SOFEA was used retrospectively to simulate concentrations of 1,3-D in air for direct comparison with monitoring program observations conducted by California Air Resources Board in Fresno County. These results indicated slight overprediction but correct magnitudes for regional air concentrations, especially at the higher percentiles, and provide a performance test. SOFEA was also used, prospectively, to predict air concentrations in potential future-use scenarios. These simulations of chronic air concentrations in two high-use 1,3-D counties of California (Ventura, Merced) consisted of 25 contiguous townships treated either at 1.5 times the current township allocation (40,937 kg) or at the maximum levels of 1,3-D used between 1999 and 2006. Exposure predictions for large regions are necessary to evaluate chronic population-based lifetime exposure and risk to 1,3-D should use patterns change. SOFEA provides a tool to estimate regional air concentrations within high-use areas required for such risk assessments.     

A standardized approach for estimating the permeability of plastic films to soil fumigants under various field and environmental conditions

Minimizing atmospheric emissions of soil fumigants is critical for protecting human and environmental health. Covering the soil surface with a plastic tarp is a common approach to restrict fumigant emissions. The mass transfer of the fumigant vapors through the tarp is often the rate-limiting factor in fumigant emissions. An approach for standardizing measurements of film permeability is proposed that is based on determining the resistance (R) of films to diffusion of fumigants. Using this approach, values were determined for more than 200 film-chemical combinations under a range of temperature, relative humidity, and film handling conditions. Resistance to diffusion was specific for each fumigant/film combination, with the largest range of values observed for the fumigant chloropicrin. For each fumigant, decreased with increasing temperature. Changes in film permeability due to increases in temperature or field installation were generally less than a factor of five. For one film, values determined under conditions of very high relative humidity (approximately 100%) were at least 100 times lower than when humidity was very low (approximately 2%). This approach simplifies the selection of appropriate films for soil fumigation by providing rapid, reproducible, and precise measurements of their permeability to specific fumigants and application conditions.     

Effect of formulation on the behavior of 1,3-dichloropropene in soil

The fumigant 1,3-dichloropropene (1,3-D) has been identified as a partial replacement for methyl bromide (CH3Br) in soil fumigation. 1,3-Dichloropropene is formulated for soil fumigation as Telone II (Dow AgroSciences, Indianapolis, IN) for shank application and as an emulsifiable concentrate (EC) (Telone EC or InLine; Dow AgroSciences) for drip application. This study investigated the effect of formulation on the phase partitioning, transformation rate, and volatilization of 1,3-D isomers. Air-water partitioning coefficients (K(H)) were slightly higher for Telone II than for Telone EC, presumably due to the higher apparent water solubility of the EC formulation. Sorption of 1,3-D isomers in two soils was not affected by formulation. Formulation had no significant effect on the rate of 1,3-D transformation in water or soil. In general, differences in the rate of 1,3-D transformation and phase partitioning due to formulation as Telone II or Telone EC were very small. Thus, the effect of formulation on 1,3-D fate may be ignored in transformation and phase partition of 1,3-D in water and soil. Packed soil columns without plastic tarp indicated that with relatively shallow subsurface (10 cm) drip application of Telone EC, emission of 1,3-D isomers was more rapid and produced greater maximum instantaneous flux than deeper (30 cm) shank injection of Telone II. Both application methods resulted in the same cumulative emissions for both isomers, 45% for (E)-1,3-D and approximately 50% for (Z)-1,3-D. These results suggest that for drip application of fumigants to be effective in reducing emissions, the fumigant must be applied at sufficient depths to prevent rapid volatilization from the soil surface if the water application rate does not sufficiently restrict vapor diffusion.     

Coupling field observations, soil modeling, and air dispersion algorithms to estimate 1,3-dichloropropene and chloropicrin flux and exposure

Soil fumigants are volatile compounds applied to agricultural land to control nematode populations, weeds, and crop diseases. Field trials used for measuring fumigant loss from soil to the atmosphere encompass only a small proportion of the near semi-infinite parameter combinations of environmental, agronomic, and meteorological conditions. One approach to supplement field observations uses a soil physics model for fumigant emission predictions. A model is first validated against existing field study observations and then used to extrapolate results to a wider range of edaphic and climatic conditions. This work compares field observations of 1,3-dichloropropene and chloropicrin emissions to predictions from the USDA soil model CHAIN_2D. Comparison between model predictions and field observations for a Florida and California study had values between 0.62 to 0.81 and 0.99 to 1.0 for discrete and cumulative emission flux, respectively. CHAIN_2D emission rates were then coupled to several USEPA air dispersion models (ISCST3, CALPUFF6) to extend emission estimates to near field air concentrations. CALPUFF6 predicted slightly higher 1-h maximum air concentrations than ISCST3 for the same source strength (26.2-36.0% for setbacks between 1 and 250 m from the field edge, respectively). A sensitivity analysis for the CHAIN_2D/ISCST3 coupled numerical system is provided, with several soil and irrigation parameters consistently the most sensitive. Changes in the depth of incorporation, tarp material, and initial soil water content illustrate the predicted impact to emission strength and resulting near-field air concentrations with reductions of cumulative emission loss from 8.1 to 71% and average 1-h maximum air concentration reductions between 6.2 and 41% depending on the mitigation strategy chosen. Additionally, a stochastic framework based on the published SOFEA system that couples variability in experiment, model sensitivity, and site specific attributes is outlined should regional air concentration estimates resulting from fumigant use be sought.     

Effect of organic material on field-scale emissions of 1,3-dichloropropene

Soil fumigation is important for growing many fruits and vegetable crops, but fumigant emissions may contaminate the atmosphere. A large-scale field experiment was initiated to test the hypothesis that adding composted municipal green waste to the soil surface in an agricultural field would reduce atmospheric emissions of the 1,3-dichloropropene (1,3-D) after shank injection at a 133 kg ha(-1) application rate. Three micrometeorological methods were used to obtain fumigant flux density and cumulative emission values. The volatilization rate was measured continuously for 16 d, and the daily peak volatilization rates for the three methods ranged from 12 to 24 μg m(-2) s(-1). The total 1,3-D mass that volatilized to the atmosphere was approximately 14 to 68 kg, or 3 to 8% of the applied active ingredient. This represents an approximately 75 to 90% reduction in the total emissions compared with other recent field, field-plot, and laboratory studies. Significant reductions in the volatilization of 1,3-D may be possible when composted municipal green waste is applied to an agricultural field. This methodology also provides a beneficial use and disposal mechanism for composted vegetative material.     

Predicting soil fumigant air concentrations under regional and diverse agronomic conditions

SOFEA (SOil Fumigant Exposure Assessment system; Dow AgroSciences, Indianapolis, IN) is a new stochastic numerical modeling tool for evaluating and managing human inhalation exposure potential associated with the use of soil fumigants. SOFEA calculates fumigant concentrations in air arising from volatility losses from treated fields for large agricultural regions using multiple transient source terms (treated fields), geographical information systems (GIS) information, agronomic specific variables, user-specified buffer zones, and field reentry intervals. A modified version of the USEPA Industrial Source Complex Short Term model (ISCST3) is used for air dispersion calculations. Weather information, field size, application date, application rate, application type, soil incorporation depth, pesticide degradation rates in air, tarp presence, field retreatment, and other sensitive parameters are varied stochastically using Monte Carlo techniques to mimic region and crop specific agronomic practices. Regional land cover, elevation, and population information can be used to refine source placement (treated fields), dispersion calculations, and risk assessments. This paper describes the technical algorithms of SOFEA and offers comparisons of simulation predictions for the soil fumigant 1,3-dichloropropene (1,3-D) to actual regional air monitoring measurements from Kern, California. Comparison of simulation results to daily air monitoring observations is remarkable over the entire concentration distribution (average percent deviation of 44% and model efficiency of 0.98), especially considering numerous inputs such as meteorological conditions for SOFEA were unavailable and approximated by neighboring regions. Both current and anticipated and/or forecasted fumigant scenarios can be simulated using SOFEA to provide risk managers and product stewards the necessary information to make sound regulatory decisions regarding the use of soil fumigants in agriculture.     

Gas-phase sorption-desorption of propargyl bromide and 1,3-dichloropropene on plastic materials

The goal of this research was to provide information for choosing appropriate materials for studying gas-phase concentrations of propargyl bromide (3BP) and 1,3-dichloropropene (1,3-D) in laboratory experiments. Several materials were tested and found to sorb both gas-phase chemicals in the following order: stainless steel (SS) < Teflon polytetrafluoroethylene (PTFE-FEP) approximately flexible polyvinyl chloride (PVC) approximately acrylic < low-density polyethylene (PE) < vinyl approximately silicone < polyurethane foam (PUF). Sorption of SS was insignificant and PUF sorbed all the fumigant that was applied. For the other materials, linear sorption coefficients (Kd) for 3BP ranged from 3.0 cm3 g(-1) for PVC to 215 cm3 g(-1) for silicone. Freundlich sorption coefficients for 1,3-D ranged from 11.5 to 371 cm3 g(-1). First-order desorption rate constants in an open system ranged from 0.05 to 1.38 h(-1) for 3BP and from 0.07 to 1.73 h(-1) for 1,3-D. In a closed system, less than 2% of sorbed fumigant desorbed from vinyl while up to 99% desorbed from PVC within 24 h when equilibrated at the highest headspace concentration. Sorption of both fumigants was linearly related to the square root of time except for vinyl and silicone. This may indicate non-fickian diffusion of fumigant into the polymer matrix. Vinyl, silicone, PE, and PUF should be avoided for quantitative study of organic gases, except possibly as a trapping medium. Use of PTFE, PVC, and acrylic may require correction for sorption-desorption and diffusion.     

Predicting methyl iodide emission, soil concentration, and pest control in a two-dimensional chamber system

Due to ever-increasing state and federal regulations, the future use of fumigants is predicted on reducing negative environmental impacts while offering sufficient pestcontrol efficacy. To foster the development of a best management practice, an integrated tool is needed to simultaneously predict fumigant movement and pest control without having to conduct elaborate and costly experiments. The objective of this study was (i) to present a two-dimensional (2-D) mathematical model to describe both fumigant movement and pestcontrol and (ii) to evaluate the model by comparing the simulated and observed results. Both analytical and numerical methods were used to predict methyl iodide (MeI) transport and fate. To predict pest control efficacy, the concentration-time index (CT) was defined and a two-parameter logistic survival model was used. Dose-response curves were experimentally determined for MeI against three types of pests (barnyardgrass [Echinochloa crus-galli] seed, citrus nematode [Tylenchulus semipenetrans], and fungi [Fusarium oxysporum]). Methyl iodide transport and pest control measurements collected from a 2-D experiimental system (60 by 60 cm) were used to test the model. Methyl iodide volatilization rates and soil gas-phase concentrations over time were accurately simulated by the model. The mass balance analysis indicates that the fraction of MeI degrading in the soil was underestimated when determined by the appearance of iodide concentration. The experimental results showed that after 24 h of MeI fumigation in the 2-D soil chamber, fungal population was not suppressed; > 90% of citrus nematodes were killed; and barnyardgrass seeds within 20-cm distance from the center were affected. These experimental results were consistent with the predicted results. The model accurately estimated the MeI movement and control of various pests and is a powerful tool to evaluate pesticides in terms of their negative environmental impacts and pest control under various environmental conditions and application methods.     

Effects of environmental factors on 1,3-dichloropropene hydrolysis in water and soil

Hydrolysis is the major pathway for fumigant 1,3-dichloropropene (1,3-D) degradation in water and soil, yet the process is not well understood. Experiments were conducted to investigate the effect of various environmental factors on the rate of 1,3-D hydrolysis. Cis-, trans-1,3-D and their isomeric mixture were spiked into water and Arlington soil (coarse-loamy, mixed, thermic Haplic Durixeralfs) and incubated under different conditions. The rate of 1,3-D hydrolysis in water and soil were evaluated based on its residual amount and Cl- release, respectively. 1,3-D hydrolyzed rapidly in deionized water, with a half-life of 9.8 d at 20 degrees C. The hydrolysis was pH dependent, with low pH inhibiting and high pH favoring the reaction. Other factors such as isomeric differences, photo irradiation, suspended particles, and small amounts of co-solutes had little effect on the reaction. In soil, 1,3-D hydrolyzed following pseudo first-order kinetics. The hydrolysis rate constant increased with soil moisture content and decreased with the initial 1,3-D concentration. At 20 degrees C, > 60% of the 1,3-D applied at < 0.61 g kg(-1) in 10% moisturized soil hydrolyzed within 30 d. The soil particle size and mineralogy had little effect on the reaction rate. Organic matter promoted 1,3-D degradation via direct substitution reactions, and the trans-isomer showed preference over the cis- to react with certain organic molecules. Microbial contributions were initially insignificant, and became important as soil microorganisms adapted to the fumigant. The results suggest that to accelerate 1,3-D degradation, pH, soil moisture, and organic amendment should be considered.     

Degradation of soil fumigants as affected by initial concentration and temperature

Soil fumigation using shank injection creates high fumigant concentration gradients in soil from the injection point to the soil surface. A temperature gradient also exists along the soil profile. We studied the degradation of methyl isothiocyanate (MITC) and 1,3-dichloropropene (1,3-D) in an Arlington sandy loam (coarse-loamy, mixed, thermic Haplic Durixeralf) at four temperatures and four initial concentrations. We then tested the applicability of first-order, half-order, and second-order kinetics, and the Michaelis-Menten model for describing fumigant degradation as affected by temperature and initial concentration. Overall, none of the models adequately described the degradation of MITC and 1,3-D isomers over the range of the initial concentrations. First-order and half-order kinetics adequately described the degradation of MITC and 1,3-D isomers at each initial concentration, with the correlation coefficients greater than 0.78 (r2> 0.78). However, the derived rate constant was dependent on the initial concentration. The first-order rate constants varied between 6 and 10x for MITC for the concentration range of 3 to 140 mg kg(-1), and between 1.5 and 4x for 1,3-D isomers for the concentration range of 0.6 to 60 mg kg(-1), depending on temperature. For the same initial concentration range, the variation in the half-order rate constants was between 1.4 and 1.7x for MITC and between 3.1 and 6.1x for 1,3-D isomers, depending on temperature. Second-order kinetics and the Michaelis-Menten model did not satisfactorily describe the degradation at all initial concentrations. The degradation of MITC and 1,3-D was primarily biodegradation, which was affected by temperature between 20 and 40 degrees C, following the Arrhenius equation (r2 > 0.74).     

Degradation of methyl isothiocyanate and chloropicrin in forest nursery soils

Recent studies have observed enhanced degradation of methyl isothiocyanate (MITC) from repeated fumigation in agricultural soils. Little is known about fumigant degradation in forest and nursery soils. This study was conducted to determine degradation rates of MITC and chloropicrin (CP) in two forest soils and the impacts of nursery management on degradation of MITC and CP. The half-life values of MITC and CP were evaluated in the laboratory under isothermal conditions (22 +/- 2 degrees C). Three rates representing 0.5x, 1x, and 2x field application rates for each fumigant were used in laboratory incubations. Effect of microbial degradation was determined by conducting incubations with both fresh and sterilized soils. Soil moisture effects were also studied. There was no difference in MITC or CP degradation between fumigated and nonfumigated forest nursery soils. Soil sterilization and high soil moisture content (15% by wt.) reduced MITC and CP degradation. The degradation rates of MITC and CP varied with factors such as nursery history, fumigant application rates, and freshness of tested soils.