United States Environmental Protection Agency Environmental Research Laboratory Athens GA 30613 Research and Development EPA/600/S3-85/051 July 1987 &EPA Project Summary Exposure Assessment Modeling for Aldicarb in Florida J. D. Dean and D. F. Atwood A modeling study was performed to assess aldicarb concentrations in drink- ing water wells in the vicinity of citrus groves in Florida. Areas in the citrus growing region were identified, with respect to the unsaturated and satu- rated zones, in which transport and transformation of aldicarb was thought to be different. In addition, an extensive literature search was conducted to determine degradation rates and adsorption coefficients for aldicarb. These regional and chemical data were used to define various simulation scenarios. The fate and migration of aldicarb was then simulated for the unsaturated zone using the Pesticide Root Zone Model and for the saturated zone using the Combined Fluid-Energy Solute Transport Model. Results of the unsaturated zone modeling showed that there were three statistically distinct scenarios with regard to pesticide leaching: "ridge" soils with thick unsaturated zones; ' 'ridge" soils with thin unsaturated zones; and ' "flatwoods" soils. The highest loads leached to ground water were approximately 1 kg/ha, occurring in areas of ' 'ridge" soils with thin unsaturated zones. Combined results of the unsaturated and saturated zone modeling showed that, in general, drinking water well concentrations should be low but may exceed 10 ppb for aldicarb. The highest simulated concentrations were in the range of 12 to 20 ppb, or three to four times the detection limit of the chem- ical (5 to 6 ppb). Highest simulated concentrations were in the surficial unconfined aquifer system, overlain with ''ridge" soils having a thin unsaturated zone. The effects of well distance from the source area also were investigated. In the surficial aquifer, with hydrogeo- logic properties most conducive to aldicarb transport, a well at 300 m (1000 ft) versus a well at 91 m (300 ft) should have from 2 to 100 times less aldicarb, depending on pesticide decay characteristics. Because of the regional scope of the study and model limitations, ' 'cata- strophic" situations such as the pres- ence of sink holes or leaky wells that would result in much higher concen- trations were not simulated. These situations are not discussed in the report. This Project Summary was devel- oped by EPA's Environmental Re- search Laboratory. Athens. GA. to announce key findings of the research project that is fully documented in a separate report of the same title (see Project Report ordering information at back). Introduction The pesticide aldicarb is used exten- sively in Florida for the control of nematodes and other pests in citrus orchards. A systemic insecticide, it is highly mobile in soils and very toxic. Evidence of aldicarb contamination in ground water in Florida prompted a March 1983 suspension of its use in all but three Florida counties. In September 1983, the use of the compound was reinstated with the restrictions that it would not be used within 90 m (300 ft) of drinking water wells and that appli- cation would be at half the label rate. To provide an assessment of the migration and fate of aldicarb in typical Florida citrus applications, a modeling ------- study was conducted with emphasis on the potential for leaching and ground- water contamination. This information can be used subsequently to perform exposure and risk assessments and to evaluate the effects of management alternatives and current use restrictions on the compound. The approach used was to collect and analyze information on compound- and site-specific factors, and then to use models to provide the interactive linkages that would result in estimation of well- water concentrations. From the chemical information, values of constants used in modeling (adsorption coefficients, decay and transformation rate coefficients, etc.) were determined. The site-specific infor- mation was used to delineate a number of scenarios that represent the likely conditions for use of the chemical and where the fate and transport behavior of the chemical can vary significantly. These scenarios may differ, for instance. because of climatic, soils or hydrogeo- logic variables in addition to chemical application and agronomic practices. The information also was used at later stages to develop model parameter sets for each scenario. Site-specific data were gathered on the Florida citrus growing region. This information collection effort was divided into two phases: characteristics of the land surface and unsaturated zone; and characteristics of the saturated zone. Factors of particular interest in the unsaturated zone were rainfall depths across region, soil hydraulic conductiv- ities and pH, and irrigation and other management practices. In the saturated zone, recharge rates, aquifer hydraulic conductivity, water table gradients, aquifer configuration, ground-water temperature and pH are of primary interest. This information was used to delineate both unsaturated and saturated zone modeling scenarios. These delineations were based on observed variations in the important factors that can result in significantly different fate and transport behavior. The chemical properties of particular interest for aldicarb are trans- formation rate coefficients for the parent compound to aldicarb sulfoxide and aldicarb sulfone, and hydrolysis rates and soil partition coefficients for each species. The Pesticide Root Zone Model (PRZM) and the Combined Fluid-Energy-Solute Transport (CFEST) model were chosen to represent the unsaturated and saturated zones, respectively. For each unsatu- rated zone scenario, PRZM was run to produce a time series and frequency distribution of pesticide loadings. These loadings were subsequently used by CFEST to produce estimates of wellwater concentrations. Within each saturated zone scenario, sensitivity to factors such as distance from source area to wells, size of source area, pesticide loading and decay rates was determined. Unsaturated Zone Results The annual pesticide loadings from 16 final unsaturated zone scenarios were analyzed in several ways. First, geomet- ric mean loadings from all scenarios were subjected to one way analysis of variance (ANOVA) to determine whether any substantive differences occurred between the mean loadings of the various scenarios. These analyses showed that, of the means of the 16 scenarios simulated, the only significant differences were among thick ridge soils (i.e., entisols and ultisols), thin ridge soils, and flatwood soils. Visual inspec- tion of the frequency distribution of annually leached pesticide loads con- firmed this. Thus, the outputs of the 16 scenarios were condensed into three scenarios: "ridge" areas with thick unsaturated zones; "ridge" areas with thin unsaturated zones; and "flatwoods" areas. The lowest loadings were associated, in general, with thick entisols and ultisols. For this scenario, there is only a 10% probability that the pesticide load leached to ground water will exceed 0.01 kg/ha. Loads from alfisols and spodosols slightly exceeded those for the thick entisols and ultisols. The highest load- ings occurred in thin unsaturated zone entisols and ultisols. There is a 10% chance that loads to ground water will exceed 0.3 kg/ha. The thickness of the unsaturated zone in this scenario is 180 cm for ultisols and 270 cm for entisols and the input load (application rate) is 5.6 kg/ha (5 Ib/acre). Increasing or decreasing the load for any of these scenarios by a factor of "x" would result in an increase or decrease in the load by the same factor. For instance, if the application rate were doubled from 5.6 kg/ha to 11.2 kg/ha, the simulated load at the 10% exceedance level in thin entisols and ultisols also would double, from 0.3 kg/ha to 0.6 kg/ha. Also of interest is the quantity of aldicarb and that of its two toxic metab- olites in the leached load. Simulations revealed that usually less than one percent of the aldicarb parent is leached to the saturated zone under any scenario. Under the thin, unsaturated zone ultisols and entisols, about 60% aldicarb sulfox- ide and 40% aldicarb sulfone makes up the leached load (a 1.5 to 1 ratio). In the thick, unsaturated zone entisols and ultisols, the ratio is closer to 0.17 to 1, sulfoxide to sulfone. For spodosols and alfisols, the ratio is roughly the same, 0.19 to 1. Obviously, because these transforma- tions are kinetically controlled, the quantity of aldicarb and its toxic metab- olites appearing in the leachate is a function of the residence time of the chemical in the profile. The sooner after application the pesticide is leached to the saturated zone, the more aldicarb and aldicarb sulfoxide will appear in the leachate. Saturated Zone Results In general, the surficial aquifer cases show the highest relative concentrations followed by the worst cases for the Floridan Aquifer and then the average casesforthe Floridan andthetwo aquifer cases. The surficial aquifer has high relative concentrations for two reasons. The relatively thin aquifer has less water for dilution of the pesticide load from the unsaturated zone. Also, the well-induced gradients and permeabilities are high enough to significantly increase the ground-water velocity to the well. This allows less time for decay. The high concentrations determined for the worst case scenarios in the Floridan Aquifer are primarily due to the high ground-water velocities that leave little time for decay or dispersion. The two-aquifer scenarios and the average Floridan scenarios have slower ground-water velocities and thicker aquifers that dilute the initial pesticide concentrations. Concentrations are higher in wells 91 m away from the source area. Even in cases with no decay, the relative con- centrations at the 300 m well are smaller because there is more dispersion. The Floridan worst cases show only a differ- ence of about 20% between the 91 m and the 300 m cases. For the average Floridan and surficial worst cases, relative concentrations are usually at least an order of magnitude smaller at the 300 m well than at the 91 m well. Again, the greater amount of time ------- required to travel to the 300 m well allows more time for decay to occur. Conclusions This modeling study was intended to provide estimates of aldicarb concentra- tions for a human health risk assess- ment. The judgment as to whether these study results represent favorable or unfavorable situations in that respect goes beyond the scope of this report. Considering the worst-case simulation scenarios and the potential uncertainties in the technical approach, this study has shown that the use of aldicarb on citrus in Florida could potentially lead to well- water concentrations exceeding 10 ppb although most estimates were much lower. The results are based on model repres- entations of generalized, regional unsat- urated and saturated zone modeling scenarios. Such a study, of necessity, overlooks specific "special situations" that may occur within these regions. To ameliorate the effects of such oversights, the general approach was to attempt to look at "worst case" values of param- eters that could be selected to describe these generalized scenarios and to adopt other "average case" values when worst cases values gave results indicative of high contamination levels. This was not done in all cases. The highest concentration simulated (in the surficial aquifer) of 20.3 ppb is within a factor of three to four of the detection limit for aldicarb and exceeds the current drinking water standard. This was for a scenario in which no pesticide decay was simulated in the saturated zone. The more realistic scenarios were those that assumed decay using the best available estimates for the degradation coefficient. The highest simulated con- centration among the decay scenarios was 0.4 ppb. This concentration was simulated in the Floridan aquifer with a shallow well 91 m from the source and in the surficial aquifer with a shallow well 91 m from the source. In both cases, the overlying soils were thin "ridge" soils. Based on results of the unsaturated zone simulations, a number of recom- mendations can be made for practices that will tend to diminish loadings from the unsaturated zone: • Avoid the application of aldicarb in ridge areas where there is a thin unsaturated zone (i.e., a high ground- water table). • Avoid the application of irrigation water in the treated soil bands' in quantities that would cause move- ment of water and pesticide past the crop root zone. • Avoid the application of irrigation water for freeze protection after the application of aldicarb to a grove. Based on the results from the satu- rated zone simulations, a number of recommendations can be made that will tend to reduce expected well-water concentrations: • Avoid application of pesticide up- gradient of wells that interest major solution cavities in areas where the aquifer is unconfined or where direct linkages exist. (This can sometimes be discovered from drilling logs.) • Avoid application near wells in the surficial aquifer that have high pump- ing rates and are closely surrounded by citrus groves. • Avoid using shallow wells where the localized induced gradient is very large. • Use of a well tapping a confined aquifer will be safer than one in an unconfined aquifer. • Use of deep wells that draw water from a large section of the aquifer will result in lower concentrations than similar wells that are shallower. Overall Project The modeling study described in this summary is part of a risk assessment performed by EPA to evaluate the poten- tial risk posed by aldicarb contamination of drinking water in Florida. Other components of the study (reported elsewhere) include a detailed monitoring of drinking water supplies and a risk assessment for populations using public and private water supply wells. ------- J. D. Dean and D. F. Atwood are with Anderson-Nichols & Co., Inc., Palo Alto, CA 94303. L. A. Mulkey is the EPA Project Officer (see below). The complete report, entitled "Exposure Assessment Modeling for Aldicarb in Florida." (Order No. PB 87-188 801/AS; Cost: $30.95) will be available only from: National Technical Information Service 5285 Port Royal Road Springfield, VA 22161 Telephone: 703-487-4650 The EPA Project Officer can be contacted at: Environmental Research Laboratory U.S. Environmental Protection Agency Athens, GA 30613 U.S. OFFICIAL MAIL' United States Environmental Protection Agency Center for Environmental Research Information Cincinnati OH 45268 Official Business Penalty for Private Use $300 EPA/600/S3-85/051 000052» ------- |