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.     

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.     

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).     

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.     

Field evaluation of a new plastic film (vapor safe) to reduce fumigant emissions and improve distribution in soil

Preplant soil fumigation is an important pest management practice in coastal California strawberry production regions. Potential atmospheric emissions of fumigants from field treatment, however, have drawn intensive environmental and human health concerns; increasingly stringent regulations on fumigant use have spurred research on low-emission application techniques. The objectives of this research were to determine the effects of a new low-permeability film, commonly known as totally impermeable film (TIF), on fumigant emissions and on fumigant distribution in soil. A 50/50 mixture of 1,3-dichloropropene (1,3-D) and chloropicrin (CP) was shank-applied at 314 kg ha in two location-separate field plots (0.4 ha each) in Ventura County, California, in fall 2009. One plot was surface-covered with standard polyethylene (PE) film, and the other was covered with TIF immediately after fumigant application. Data collection included emissions, soil-gas phase concentration profile, air concentration under the film, and soil residuals of the applied fumigants. Peak emission flux of 1,3-D and CP from the TIF field was substantially lower than from the PE field. Total through-film emission loss was 2% for 1,3-D and <1% for CP from the TIF field during a 6-d film covering period, compared with 43% for 1,3-D and 12% for CP from the PE field. However, on film-cutting, greater retention of 1,3-D in the TIF field resulted in a much higher emission surge compared with the PE field, while CP emissions were fairly low in both fields. Higher concentrations and a more uniform distribution in the soil profile for 1,3-D and CP were observed under the TIF compared with the PE film, suggesting that the TIF may allow growers to achieve satisfactory pest control with lower fumigant rates. The surging 1,3-D emissions after film-cutting could result in high exposure risks to workers and bystanders and must be addressed with additional mitigation measures.     

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.     

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.     

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.     

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.     

Regional assessment of herbicide sorption and degradation in two sampling years

Sorption and degradation of the herbicide 2,4-D [2,4-dichlorophenoxyacetic acid] were determined for 123 surface soils (0 to 15 cm) collected in 2002 and in 2004 between 49 degrees to 60 degrees north longitude and 110 degrees to 120 degrees west latitude in Alberta, Canada. The soils were characterized by soil organic carbon content (SOC), pH, electrical conductivity, soil texture, cation exchange capacity, carbonate content, and total soil microbial activity. The 2,4-D sorption coefficients, Kd and Koc, were highly variable with coefficients of variation of 89 and 59%, respectively, at the provincial scale. Both Kd and Koc were well described by regression models with SOC and soil pH as variables, regardless of scale. Surprisingly, variations in 2,4-D mineralization were much smaller than variations in sorption. Variability in total 2,4-D mineralization was particularly low, with a coefficient of variation of only 7% at the provincial scale. Average 2,4-D half-lives in ecoregions ranged from 1.7 to 3.5 d, much lower than the field dissipation half-life of 10 d reported for 2,4-D in general pesticide property databases. Regression models describing degradation parameters were generally poor or not significant because 2,4-D mineralization was only weakly associated with measured 2,4-D sorption parameters and soil properties. As such, regional variations in herbicide sorption coefficients should be measured or calculated based on soil properties, to assign distinct pesticide fate model input parameters when estimating 2,4-D off-site transport at the provincial scale. Spatial variations in herbicide degradation appear less important for Alberta as 2,4-D half-lives were similar in soils across the province. The rapid mineralization of 2,4-D is noteworthy because 2,4-D is widely used in Alberta and perhaps adaptation of soil microbial communities allowed for accelerated degradation regardless of soil properties or the extent of 2,4-D sorption by soil.     

Volatilization and degradation of soil-applied dimethylselenide

Dimethylselenide (DMSe) is a highly volatile gas that is produced by indigenous microorganisms in seleniferous soils and sediments; however, little is known about the soil conditions that affect the persistence of DMSe and its transport to the atmosphere. In this study we investigated the effect of moisture content, temperature, and organic amendments on the degradation of soil-applied DMSe. The degradation of DMSe was entirely a result of biological mechanisms, but changes in temperature (20-40 degrees C) and soil moisture content (30-70% of the maximum water holding capacity) had little influence on the degradation rate. In contrast, amending soil with either 1% casein or gluten (by weight) had an inhibitory effect on the degradation of DMSe. After 18 d, 2.1 times more DMSe was present in the casein-amended soil and 2.6 times more DMSe was present in the gluten-amended soil. The transport of DMSe in packed soil columns was also investigated. Increasing the depth to soil surface was found to significantly decrease the amount of DMSe transported to the air. After 6 d, 57% of DMSe injected 10 cm below the soil surface was volatilized. At an injection depth of 20 cm the cumulative emissions were reduced by 38% and at 30 cm the cumulative emissions were reduced by 51%. In columns containing 1% casein or gluten in the top 5 cm of soil the cumulative loss of DMSe was about 9% higher than in unamended soil. Increasing our understanding of the soil conditions that influence the gaseous diffusion of DMSe should help in determining the feasibility of using Se volatilization as a remediation technique.     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

Quantification of the effect of fumigation on short- and long-term nitrogen mineralization and nitrification in different soils

The effect of soil fumigation on N mineralization and nitrification needs to be better quantified to optimize N fertilizer advice and predict NO(-)(3) concentrations in crops and NO(-)(3) leaching risks. Seven soils representing a range in soil texture and organic matter contents were fumigated with Cyanamid DD 95 (a mixture of 1,3-dichloropropane and 1,3-dichloropropene). After removal of the fumigant, the fumigated soils and unfumigated controls were incubated for 20 wk and N mineralization and nitrification were monitored by destructive sampling. The average short-term N mineralization rates (k(s)) were significantly larger in the fumigated than in the unfumigated soils (P = 0.025), but the differences in k(s) between fumigated and unfumigated soils could not be related to soil properties. The average long-term N mineralization rates (k(l)) were slightly larger in the fumigated soils but the difference with the unfumigated soils was not significant. Again, the differences in k(l) values could not be related to soil properties. Nitrification was inhibited completely for at least 3 wk in all soils, and an effect on nitrification could be observed up to 17 wk in one soil. An S-shaped function was fitted to the nitrification data corrected for N mineralization, and both the rate constant (gamma) and the time at which maximum nitrification was reached (t(max)) were strongly correlated to soil pH. However, since no correlations were found between the effect of fumigation on N mineralization and soil properties, taking into account the effects of fumigation in fertilizer advice and in the prediction of NO(-)(3) leaching risks will need further research.     

Environmental fate of triasulfuron in soils amended with municipal waste compost

The amendment of soil with compost may significantly influence the mobility and persistence of pesticides and thus affect their environmental fate. Factors like adsorption, kinetics, and rate of degradation of pesticides could be altered in amended soils. The aim of this study was to determine the effects of the addition of compost made from source-separated municipal waste and green waste, on the fate of triasulfuron [(2-(2-chloroethoxy)-N-[[4-methoxy-6-methyl-1,3,5-triazin-2-yl)amino]carbonyl]benzenesulfonamide], a sulfonylurea herbicide used in postemergence treatment of cereals. Two native soils with low organic matter content were used. A series of analyses was performed to evaluate the adsorption and degradation of the herbicide in soil and in solution after the addition of compost and compost-extracted organic fractions, namely humic acids (HA), fulvic acids (FA), and hydrophobic dissolved organic matter (HoDOM). Results have shown that the adsorption of triasulfuron to soil increases in the presence of compost, and that the HA and HoDOM fractions are mainly responsible for this increase. Hydrophobic dissolved organic matter applied to the soils underwent sorption reactions with the soils, and in the sorbed state, served to increase the adsorption capacity of the soil for triasulfuron. The rate of hydrolysis of triasulfuron in solution was significantly higher at acidic pH and the presence of organic matter fractions extracted from compost also slightly increased the rate of hydrolysis. The rate of degradation in amended and nonamended soils is explained by a two-stage degradation kinetics. During the initial phase, although triasulfuron degradation was rapid with a half-life of approximately 30 d, the presence of compost and HoDOM was found to slightly reduce the rate of degradation with respect to that in nonamended soil.