Comparison of regional air dispersion simulation and ambient air monitoring data for the soil fumigant 1,3-dichloropropene.

SOFEA v2.0 is an air dispersion modeling tool used to predict acute and chronic pesticide concentrations in air for large air sheds resulting from agronomic practices. A 1,3-dichloropropene (1,3-D) air monitoring study in high use townships in Merced County, CA, logged 3-day average air concentrations at nine locations over a 14.5month period. SOFEA, using weather data measured at the site, and using a historical CDPR regulatory assumption of a constant 320m mixing height, predicted the general pattern and correct order of magnitude for 1,3-D air concentrations as a function of time, but failed to estimate the highest observed 1,3-D concentrations of the monitoring study. A time series and statistical comparison of the measured and modeled data indicated that the model underestimated 1,3-D concentrations during calm periods (wind speed <1m/s), such that the annual average concentration was under predicted by approximately 4.7-fold, and the variability was not representative of the measured data. Calm periods are associated with low mixing heights (MHs) and are more prevalent in the Central Valley of CA during the winter months, and thus the assumption of a constant 320m mixing height is not appropriate. An algorithm was developed to calculate the MH using the air temperature in the weather file when the wind speed was <1m/s. When the model was run using the revised MHs, the average of the modeled 1,3-D concentration Probability Distribution Function (PDF) was within 5% of the measured PDF, and the variability in modeled concentrations more closely matched the measured dataset. Use of the PCRAMMET processed weather data from the site (including PCRAMMET MH) resulted in the global annual average concentration within 2-fold of measured data. Receptor density was also found to have an effect on the modeled 1,3-D concentration PDF, and a 50×50 receptor grid in the nine township domain captured the measured 1,3-D concentration distribution much better than a 3×3 receptor grid (i.e., simulated receptors at the nine monitoring locations). Comparison of the monitored and simulated PDF for 72-h 1,3-D concentrations indicated that SOFEA slightly over predicts the 1,3-D concentration distribution at all percentiles below the 99th with slight under prediction of the 99-100th percentile values. This suggests that without further refinement, the SOFEA2 model, based upon field validation observations, will result in representative but conservative estimates of lifetime exposure to 1,3-D for bystanders in 1,3-D use areas.

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.

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.

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 regional emissions and near-field air concentrations of soil fumigants using modest numerical algorithms: a case study using 1,3-dichloropropene.

Soil fumigants, used to control nematodes and crop disease, can volatilize from the soil application zone and into the atmosphere to create the potential for human inhalation exposure. An objective for this work is to illustrate the ability of simple numerical models to correctly predict pesticide volatilization rates from agricultural fields and to expand emission predictions to nearby air concentrations for use in the exposure component of a risk assessment. This work focuses on a numerical system using two U.S. EPA models (PRZM3 and ISCST3) to predict regional volatilization and nearby air concentrations for the soil fumigant 1,3-dichloropropene. New approaches deal with links to regional databases, seamless coupling of emission and dispersion models, incorporation of Monte Carlo sampling techniques to account for parametric uncertainty, and model input sensitivity analysis. Predicted volatility flux profiles of 1,3-dichloropropene (1,3-D) from soil for tarped and untarped fields were compared against field data and used as source terms for ISCST3. PRZM3 can successfully estimate correct order of magnitude regional soil volatilization losses of 1,3-D when representative regional input parameters are used (soil, weather, chemical, and management practices). Estimated 1,3-D emission losses and resulting air concentrations were investigated for five geographically diverse regions. Air concentrations (15-day averages) are compared with the current U.S. EPA's criteria for human exposure and risk assessment to determine appropriate setback distances from treated fields. Sensitive input parameters for volatility losses were functions of the region being simulated.

Terrestrial field dissipation of diclosulam at four sites in the United States.

The soil dissipation of diclosulam was studied using 14C-labeled and nonradiolabeled material in Mississippi, North Carolina, Georgia, and Illinois between 1994 and 1997. The test substance was preemergence broadcast applied at target rates of 35 and 37 g ai x ha(-1) for the 14C-labeled and the nonradiolabeled studies, respectively. The degradation of diclosulam was rapid with half-lives ranging from 13 to 43 days at the four sites. Rapid degradation rates and the increasing sorption to soil over time resulted in low persistence and mobility of this compound. Metabolite formation and dissipation in the field reflected observations of photolysis, hydrolysis, and aerobic soil metabolism studies in the laboratory. The rapid field dissipation rates, metabolite formation patterns, and sorption characteristics obtained in these field studies were consistent with the laboratory data generated for diclosulam, and reflect the multiple concurrent degradation mechanisms occurring in the field.

Biodegradation kinetics for pesticide exposure assessment.

Understanding pesticide risks requires characterizing pesticide exposure within the environment in a manner that can be broadly generalized across widely varied conditions of use. The coupled processes of sorption and soil degradation are especially important for understanding the potential environmental exposure of pesticides. The data obtained from degradation studies are inherently variable and, when limited in extent, lend uncertainty to exposure characterization and risk assessment. Pesticide decline in soils reflects dynamically coupled processes of sorption and degradation that add complexity to the treatment of soil biodegradation data from a kinetic perspective. Additional complexity arises from study design limitations that may not fully account for the decline in microbial activity of test systems, or that may be inadequate for considerations of all potential dissipation routes for a given pesticide. Accordingly, kinetic treatment of data must accommodate a variety of differing approaches starting with very simple assumptions as to reaction dynamics and extending to more involved treatments if warranted by the available experimental data. Selection of the appropriate kinetic model to describe pesticide degradation should rely on statistical evaluation of the data fit to ensure that the models used are not overparameterized. Recognizing the effects of experimental conditions and methods for kinetic treatment of degradation data is critical for making appropriate comparisons among pesticide biodegradation data sets. Assessment of variability in soil half-life among soils is uncertain because for many pesticides the data on soil degradation rate are limited to one or two soils. Reasonable upper-bound estimates of soil half-life are necessary in risk assessment so that estimated environmental concentrations can be developed from exposure models. Thus, an understanding of the variable and uncertain distribution of soil half-lives in the environment is necessary to estimate bounding values. Statistical evaluation of measures of central tendency for multisoil kinetic studies shows that geometric means better represent the distribution in soil half-lives than do the arithmetic or harmonic means. Estimates of upper-bound soil half-life values based on the upper 90% confidence bound on the geometric mean tend to accurately represent the upper bound when pesticide degradation rate is biologically driven but appear to overestimate the upper bound when there is extensive coupling of biodegradation with sorptive processes. The limited data available comparing distribution in pesticide soil half-lives between multisoil laboratory studies and multilocation field studies suggest that the probability density functions are similar. Thus, upper-bound estimates of pesticide half-life determined from laboratory studies conservatively represent pesticide biodegradation in the field environment for the purposes of exposure and risk assessment. International guidelines and approaches used for interpretations of soil biodegradation reflect many common elements, but differ in how the source and nature of variability in soil kinetic data are considered. Harmonization of approaches for the use of soil biodegradation data will improve the interpretative power of these data for the purposes of exposure and risk assessment.

Measurement and modeling of diclosulam runoff under the influence of simulated severe rainfall.

A runoff study was conducted near Tifton, GA to measure the losses of water, sediment, and diclosulam (N-(2,6-dichlorophenyl)-5-ethoxy-7-fluoro-[1,2,4]triazolo-[1,5c]-pyrimidine- 2-sulfonamide), a new broadleaf herbicide, under a 50-mm-in-3-h simulated rainfall event on three separate 0.05-ha plots. Results of a runoff study were used to validate the Pesticide Root Zone Model (PRZM, v. 3.12) using field-measured soil, chemical, and weather inputs. The model-predicted edge-of-field diclosulam loading was within 1% of the average observed diclosulam runoff from the field study; however, partitioning between phases was not as well predicted. The model was subsequently used with worst-case agricultural practice inputs and a 41-yr weather record from Dublin, GA to simulate edge-of-field runoff losses for the two most prevalent soils (Tifton and Bibb) in the southeastern U.S. peanut (Arachis hypogaea L.) market for 328 simulation years, and showed that the 90th percentile runoff amounts, expressed as percent of applied diclosulam, were 1.8, 0.6, and 5.2% for the runoff study plots and Tifton and Bibb soils, respectively. The runoff study and modeling indicated that more than 97% of the total diclosulam runoff was transported off the field by water, with < 3% associated with the sediment. Diclosulam losses due to runoff can be further reduced by lower application rates, tillage and crop residue management practices that reduce edge-of-field runoff, and conservation practices such as vegetated filter strips.

Tillage, intercrop, and controlled drainage-subirrigation influence atrazine, metribuzin, and metolachlor loss.

Atrazine (6-chloro-N2-ethyl-N4-isopropyl-1,3,5-triazine-2,4-diamine) and metolachlor [2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methylethyl)acetamide] have been found with increasing occurrence in rivers and streams. Their continued use will require changes in agricultural practices. We compared water quality from four crop-tillage treatments: (i) conventional moldboard plow (MB), (ii) MB with ryegrass (Lolium multiflorum Lam.) intercrop (IC), (iii) soil saver (SS), and (iv) SS + IC; and two drainage control treatments, drained (D) and controlled drainage-subirrigation (CDS). Atrazine (1.1 kg a.i. ha-1), metribuzin [4-amino-6-(1,1-dimethylethyl)-3-(methylthio)-1,2,4-triazine-5(4H)-one] (0.5 kg a.i. ha-1), and metolachlor (1.68 kg a.i. ha-1) were applied preemergence in a band over seeded corn (Zea mays L.) rows. Herbicide concentration and losses were monitored from 1992 to spring 1995. Annual herbicide losses ranged from < 0.3 to 2.7% of application. Crop-tillage treatment influenced herbicide loss in 1992 but not in 1993 or 1994, whereas CDS affected partitioning of losses in most years. In 1992, SS + IC reduced herbicide loss in tile drains and surface runoff by 46 to 49% compared with MB. The intercrop reduced surface runoff, which reduced herbicide transport. Controlled drainage-subirrigation increased herbicide loss in surface runoff but decreased loss through tile drainage so that total herbicide loss did not differ between drainage treatments. Desethyl atrazine [6-chloro-N-(1-methylethyl)-1,3,5-triazine-2,4-diamine] comprised 7 to 39% of the total triazine loss.

Predicted 1,3-dichloropropene air concentrations resulting from tree and vine applications in California.

The preplant soil fumigant 1,3-dichloropropene (1,3-D) is effective for nematode control and is expected to further replace methyl bromide (MeBr) as MeBr use is phased out. Acute human exposure to soil fumigants is managed in part by using buffer zones between treated fields and occupied structures. The required buffer zone for 1,3-D in California is 91.4 m (300 ft) for all uses. However, a 30.5-m (100-ft) buffer setback is desired for 1,3-D to be an important replacement for MeBr in the orchard and vineyard markets. The Industrial Source Complex Short-Term model, Version 3 (ISCST3) was used to simulate township-wide long-term average and short-term air concentration distributions of 1,3-D. The Gaussian plume model ISCST3 can be used to assess dispersion of air pollutants and pollutant concentrations on receptors from a variety of sources and in diverse airsheds. Long-term and daily-average air concentrations can be compared with the California permitted chronic or acute toxicity endpoints, respectively, to assess the potential risk for individuals living within the township at the proposed buffer setback. Modifications to ISCST3 were made for specific nonpoint-source agricultural constraints and management practices. Chronic and acute air concentration distributions of 1,3-D with a 30.5-m buffer constraint around treated fields are similar to currently permitted air concentration distributions in California. Refinement of exposure as a function of buffer distance, application rate, and field size is possible due to the resolution of the simulation and external post-processing capabilities. Simulated examples of 1,3-D acute and chronic exposure cumulative distributions are presented.