Foliar and soil deposition of pesticide sprays in peanuts and their washoff and runoff under simulated worst-case rainfall conditions.

There are few studies that relate the timing and amounts of pesticide washoff from plant foliage during rainfall to runoff losses at the edge of the field. We hypothesized that foliar deposits, if washed onto the soil slowly during rainfall, may then undergo less leaching during the period of infiltration that occurs prior to soil saturation and runoff, thus exhibiting larger runoff losses than pesticides on/in the soil at the beginning of rain. We measured the runoff of ethalfluralin, metolachlor, chlorothalonil, and rhodamine WT dye using simulated rainfall on 450 m2 mesoplots planted in peanut. Ethalfluralin was applied preplant incorporated, and metolachlor was applied preemergence on bare soil. Chlorothalonil and rhodamine WT were applied to the peanut canopy at maturity. Rainfall was simulated 24 h after each chemical application (in May and July, 1998, and May and August, 1999) using raindrop sprinklers, applying 5.5 +/- 0.5 cm over a 2 h period to create reasonable worst-case conditions; between 3 and 9 mm of runoff was generated. Volume-weighted average concentrations of chemicals in runoff were 7, 104, 163, and 179 ug L(-1) for ethalfluralin, metolachlor, chlorothalonil, and rhodamine WT, respectively. The total amounts of chemicals lost in the runoff events were 0.04 +/- 0.01, 0.2 +/- 0.1, 0.6 +/- 0.5, and 0.2 +/- 0.1, as percents of amounts applied, respectively. Rhodamine WT formed a vivid red solution on wetting and provided visual clues to the dynamics of chemical washoff/runoff. The washoff from rain-exposed peanut foliage appeared to be complete within a few minutes of the beginning of rainfall, and disappearance of dye from rain-exposed soil surface occurred within the first 10 min of rainfall. However, dye was present in runoff water at near-constant concentrations throughout the 2 h runoff event, indicating that near-constant amounts of chemical remained in the soil extraction zone. These results confirm earlier studies showing that soil incorporation at application significantly reduces runoff losses and that a majority of foliar residues can be washable if rainfall occurs within a few days after application. Runoff losses of foliar-applied pesticides were small relative to washoff amounts but were sensitive to runoff timing relative to washoff.

Application of the Root Zone Water Quality Model (RZWQM) to pesticide fate and transport: an overview.

Pesticide transport models are tools used to develop improved pesticide management strategies, study pesticide processes under different conditions (management, soils, climates, etc) and illuminate aspects of a system in need of more field or laboratory study. This paper briefly overviews RZWQM history and distinguishing features, overviews key RZWQM components and reviews RZWQM validation studies. RZWQM is a physically based agricultural systems model that includes sub-models to simulate: infiltration, runoff, water distribution and chemical movement in the soil; macropore flow and chemical movement through macropores; evapotranspiration (ET); heat transport; plant growth; organic matter/nitrogen cycling; pesticide processes; chemical transfer to runoff; and the effect of agricultural management practices on these processes. Research to date shows that if key input parameters are calibrated, RZWQM can adequately simulate the processes involved with pesticide transport (ET, soil-water content, percolation and runoff, plant growth and pesticide fate). A review of the validation studies revealed that (1) accurate parameterization of restricting soil layers (low permeability horizons) may improve simulated soil-water content; (2) simulating pesticide sorption kinetics may improve simulated soil pesticide concentration with time (persistence) and depth and (3) calibrating the pesticide half-life is generally necessary for accurate pesticide persistence simulations. This overview/review provides insight into the processes involved with the RZWQM pesticide component and helps identify model weaknesses, model strengths and successful modeling strategies.

Documenting the pesticide processes module of the ARS RZWQM agroecosystem model.

We describe the theory and current development state of the pesticide process module of the USDA-Agricultural Research Service Root Zone Water Quality Model, or RZWQM. Several processes which are significant in determining the fate of a pesticide application are included together in this module for the first time, including application technique, root uptake, ionic dissociation, soil depth dependence of persistence, volatilization, wicking upward in soil and aging of residues. The pesticide module requires a large number of parameters to run (as does the RZWQM model as a whole) and it is becoming clear that RZWQM will find most interest and use as part of a 'scenario' in which all data requirements are supplied and the predictions of the system compared with a real (usually partial) data set. Such a scenario may then be modified to examine the response of the system to changes in inputs. It also has significant potential as a technology transfer or teaching tool, providing detailed understanding of a specific agronomic system and its potential impacts on the environment.

The pesticide module of the Root Zone Water Quality Model (RZWQM): testing and sensitivity analysis of selected algorithms for pesticide fate and surface runoff.

The Root Zone Water Quality Model (RZWQM) is a one-dimensional, numerical model for simulating water movement and chemical transport under a variety of management and weather scenarios at the field scale. The pesticide module of RZWQM includes detailed algorithms that describe the complex interactions between pesticides and the environment. We have simulated a range of situations with RZWQM, including foliar interception and washoff of a multiply applied insecticide (chlorpyrifos) to growing corn, and herbicides (alachlor, atrazine, flumetsulam) with pH-dependent soil sorption, to examine whether the model appears to generate reasonable results. The model was also tested using chlorpyrifos and flumetsulam for the sensitivity of its predictions of chemical fate and water and pesticide runoff to various input parameters. The model appears to generate reasonable representations of the fate and partitioning of surface- and foliar-applied chemicals, and the sorption of weakly acidic or basic pesticides, processes that are becoming increasingly important for describing adequately the environmental behavior of newer pesticides. However, the kinetic sorption algorithms for charged pesticides appear to be faulty. Of the 29 parameters and variables analyzed, chlorpyrifos half-life, the Freundlich adsorption exponent, the fraction of kinetic sorption sites, air temperature, soil bulk density, soil-water content at 33 kPa suction head and rainfall were most sensitive for predictions of chlorpyrifos residues in soil. The latter three inputs and the saturated hydraulic conductivity of the soil and surface crusts were most sensitive for predictions of surface water runoff and water-phase loss of chlorpyrifos. In addition, predictions of flumetsulam (a weak acid) runoff and dynamics in soil were sensitive to the Freundlich equilibrium adsorption constant, soil pH and its dissociation coefficient.

Modeling hydrology, metribuzin degradation and metribuzin transport in macroporous tilled and no-till silt loam soil using RZWQM.

Due to the complex nature of pesticide transport, process-based models can be difficult to use. For example, pesticide transport can be effected by macropore flow, and can be further complicated by sorption, desorption and degradation occurring at different rates in different soil compartments. We have used the Root Zone Water Quality Model (RZWQM) to investigate these phenomena with field data that included two management conditions (till and no-till) and metribuzin concentrations in percolate, runoff and soil. Metribuzin degradation and transport were simulated using three pesticide sorption models available in RZWQM: (a) instantaneous equilibrium-only (EO); (b) equilibrium-kinetic (EK, includes sites with slow desorption and no degradation); (c) equilibrium-bound (EB, includes irreversibly bound sites with relatively slow degradation). Site-specific RZWQM input included water retention curves from four soil depths, saturated hydraulic conductivity from four soil depths and the metribuzin partition coefficient. The calibrated parameters were macropore radius, surface crust saturated hydraulic conductivity, kinetic parameters, irreversible binding parameters and metribuzin half-life. The results indicate that (1) simulated metribuzin persistence was more accurate using the EK (root mean square error, RMSE = 0.03 kg ha(-1)) and EB (RMSE = 0.03 kg ha(-1)) sorption models compared to the EO (RMSE = 0.08 kg ha(-1)) model because of slowing metribuzin degradation rate with time and (2) simulating macropore flow resulted in prediction of metribuzin transport in percolate over the simulation period within a factor of two of that observed using all three pesticide sorption models. Moreover, little difference in simulated daily transport was observed between the three pesticide sorption models, except that the EB model substantially under-predicted metribuzin transport in runoff and percolate >30 days after application when transported concentrations were relatively low. This suggests that when macropore flow and hydrology are accurately simulated, metribuzin transport in the field may be adequately simulated using a relatively simple, equilibrium-only pesticide model.

Test of the Root Zone Water Quality Model (RZWQM) for predicting runoff of atrazine, alachlor and fenamiphos species from conventional-tillage corn mesoplots.

The Root Zone Water Quality Model (RZWQM) is a comprehensive, integrated physical, biological and chemical process model that simulates plant growth and movement of water, nutrients and pesticides in a representative area of an agricultural system. We tested the ability of RZWQM to predict surface runoff losses of atrazine, alachlor, fenamiphos and two fenamiphos oxidative degradates against results from a 2-year mesoplot rainfall simulation experiment. Model inputs included site-specific soil properties and weather, but default values were used for most other parameters, including pesticide properties. No attempts were made to calibrate the model except for soil crust/seal hydraulic conductivity and an adjustment of pesticide persistence in near-surface soil. Approximately 2.5 (+/- 0.9), 3.0 (+/- 0.8) and 0.3 (+/- 0.2)% of the applied alachlor, atrazine and fenamiphos were lost in surface water runoff, respectively. Runoff losses in the 'critical' events--those occurring 24 h after pesticide application--were respectively 91 (+/- 5), 86 (+/- 6) and 96 (+/- 3)% of total runoff losses for these pesticides. RZWQM adequately predicted runoff water volumes, giving a predicted/observed ratio of 1.2 (+/- 0.5) for all events. Predicted pesticide concentrations and loads from the 'critical' events were generally within a factor of 2, but atrazine losses from these events were underestimated, which was probably a formulation effect, and fenamiphos losses were overestimated due to rapid oxidation. The ratios of predicted to measured pesticide concentrations in all runoff events varied between 0.2 and 147, with an average of 7. Large over-predictions of pesticide runoff occurred in runoff events later in the season when both loads and concentrations were small. The normalized root mean square error for pesticide runoff concentration predictions varied between 42 and 122%, with an average of 84%. Pesticide runoff loads were predicted with a similar accuracy. These results indicate that the soil-water mixing model used in RZWQM is a robust predictor of pesticide entrainment and runoff.

Herbicide leaching as affected by macropore flow and within-storm rainfall intensity variation: a RZWQM simulation.

Within-event variability in rainfall intensity may affect pesticide leaching rates in soil, but most laboratory studies of pesticide leaching use a rainfall simulator operating at constant rainfall intensity, or cover the soil with ponded water. This is especially true in experiments where macropores are present--macroporous soils present experimental complexities enough without the added complexity of variable rainfall intensity. One way to get around this difficulty is to use a suitable pesticide transport model, calibrate it to describe accurately a fixed-intensity experiment, and then explore the affects of within-event rainfall intensity variation on pesticide leaching through macropores. We used the Root Zone Water Quality Model (RZWQM) to investigate the effect of variable rainfall intensity on alachlor and atrazine transport through macropores. Data were used from an experiment in which atrazine and alachlor were surface-applied to 30 x 30 x 30 cm undisturbed blocks of two macroporous silt loam soils from glacial till regions. One hour later the blocks were subjected to 30-mm simulated rain with constant intensity for 0.5 h. Percolate was collected and analyzed from 64 square cells at the base of the blocks. RZWQM was calibrated to describe accurately the atrazine and alachlor leaching data, and then a median Mid-west variable-intensity storm, in which the initial intensity was high, was simulated. The variable-intensity storm more than quadrupled alachlor losses and almost doubled atrazine losses in one soil over the constant-intensity storm of the same total depth. Also rainfall intensity may affect percolate-producing macroporosity and consequently pesticide transport through macropores. For example, under variable rainfall intensity RZWQM predicted the alachlor concentration to be 2.7 microg ml(-1) with an effective macroporosity of 2.2 E(-4) cm(3) cm(-3) and 1.4 microg ml(-1) with an effective macroporosity of 4.6 E(-4) cm(3) cm(-3). Percolate-producing macroporosity and herbicide leaching under different rainfall intensity patterns, however, are not well understood. Clearly, further investigation of rainfall intensity variation on pesticide leaching through macropores is needed.

Software for pest-management science: computer models and databases from the United States Department of Agriculture-Agricultural Research Service.

We present an overview of USDA Agricultural Research Service (ARS) computer models and databases related to pest-management science, emphasizing current developments in environmental risk assessment and management simulation models. The ARS has a unique national interdisciplinary team of researchers in surface and sub-surface hydrology, soil and plant science, systems analysis and pesticide science, who have networked to develop empirical and mechanistic computer models describing the behavior of pests, pest responses to controls and the environmental impact of pest-control methods. Historically, much of this work has been in support of production agriculture and in support of the conservation programs of our 'action agency' sister, the Natural Resources Conservation Service (formerly the Soil Conservation Service). Because we are a public agency, our software/database products are generally offered without cost, unless they are developed in cooperation with a private-sector cooperator. Because ARS is a basic and applied research organization, with development of new science as our highest priority, these products tend to be offered on an 'as-is' basis with limited user support except for cooperating R&D relationship with other scientists. However, rapid changes in the technology for information analysis and communication continually challenge our way of doing business.

Interlaboratory comparison of extraction efficiency of pesticides from surface and laboratory water using solid-phase extraction disks.

A continuation of an earlier interlaboratory comparison was conducted (1) to assess solid-phase extraction (SPE) using Empore disks to extract atrazine, bromacil, metolachlor, and chlorpyrifos from various water sources accompanied by different sample shipping and quantitative techniques and (2) to compare quantitative results of individual laboratories with results of one common laboratory. Three replicates of a composite surface water (SW) sample were fortified with the analytes along with three replicates of deionized water (DW). A nonfortified DW sample and a nonfortified SW sample were also extracted. All samples were extracted using Empore C(18) disks. After extraction, part of the samples were eluted and analyzed in-house. Duplicate samples were evaporated in a 2-mL vial, shipped dry to a central laboratory (SDC), redissolved, and analyzed. Overall, samples analyzed in-house had higher recoveries than SDC samples. Laboratory x analysis type and laboratory x water source interactions were significant for all four compounds. Seven laboratories participated in this interlaboratory comparison program. No differences in atrazine recoveries were observed from in-house samples analyzed by laboratories A, B, D, and G compared with the recovery of SDC samples. In-house atrazine recoveries from laboratories C and F were higher when compared with recovery from SDC samples. However, laboratory E had lower recoveries from in-house samples compared with SDC samples. For each laboratory, lower recoveries were observed for chlorpyrifos from the SDC samples compared with samples analyzed in-house. Bromacil recovery was <65% at two of the seven laboratories in the study. Bromacil recoveries for the remaining laboratories were >75%. Three laboratories showed no differences in metolachlor recovery; two laboratories had higher recoveries for samples analyzed in-house, and two other laboratories showed higher metolachlor recovery for SDC samples. Laboratory G had a higher recovery in SW for all four compounds compared with DW. Other laboratories that had significant differences in pesticide recovery between the two water sources showed higher recovery in DW than in the SW regardless of the compound. In comparison to earlier work, recovery of these compounds using SPE disks as a temporary storage matrix may be more effective than shipping dried samples in a vial. Problems with analytes such as chlorpyrifos are unavoidable, and it should not be assumed that an extraction procedure using SPE disks will be adequate for all compounds and transferrable across all chromatographic conditions.

Interlaboratory comparison of pesticide recovery from water using solid-phase extraction disks and gas chromatography.

An interlaboratory study was conducted to assess the suitability of C18 solid-phase extraction disks to retain and ship different pesticides from water samples. Surface and deionized water samples were fortified with various pesticides and extracted using C18 disks. Pesticides were eluted from disks and analyzed in-house, or disks were sent to another laboratory where they were eluted and analyzed. Along with the disks, a standard pesticide solution in methanol was also shipped to be used for fortification, extraction, and analysis. The highest recovery from deionized or surface water using shipped disks was obtained for cyanazine (>97%), followed by metalaxyl (>96%), and atrazine (>92%). Although <40% of the bifenthrin, chlorpyrifos, and chlorothalonil fortified in surface water was recovered from shipped disks, recoveries from deionized water were >70%. From in-house eluted disks, bifenthrin and chlorpyrifos were recovered at 118 and 105%, whereas chlorothalonil showed 71% recovery, indicating that poor recovery from surface water was due to loss during shipping rather than low retention by the C18 disks. There was no consistent relationship between recovery from C18 disk and physicochemical properties for the pesticides included in this study. For most of the 13 pesticides tested, there were no differences in recovery between in-house extracted disks and shipped disks, indicating the suitability of disks to concentrate and transport pesticides extracted from water samples.

Pesticide soil sorption parameters: theory, measurement, uses, limitations and reliability.

The soil sorption coefficient Kd and the soil organic carbon sorption coefficient KOC of pesticides are basic parameters used by environmental scientists and regulatory agencies worldwide in describing the environmental fate and behavior of pesticides. They are a measure of the strength of sorption of pesticides to soils and other geosorbent surfaces at the water/solid interface, and are thus directly related to both environmental mobility and persistence. KOC is regarded as a 'universal' parameter related to the hydrophobicity of the pesticide molecule, which applies to a given pesticide in all soils. This assumption is known to be inexact, but it is used in this way in modeling and estimating risk for pesticide leaching and runoff. In this report we examine the theory, uses, measurement or estimation, limitations and reliability of these parameters and provide some 'rules of thumb' for the use of these parameters in describing the behavior and fate of pesticides in the environment, especially in analysis by modeling.

Persistence and runoff losses of 3 herbicides and chlorpyrifos from a corn field in the Lake Balaton watershed of Hungary.

Corn is intensively cultivated in western Hungary in the basin of Lake Balaton, one of the most important water resources in eastern Europe. Pesticide runoff was measured in 1996 and 1997 from a typical corn field near Zalaegerszeg, Hungary, which drains into the Zala River, an important water source of Lake Balaton. Three herbicides, namely atrazine, acetochlor, and propizochlor, and the insecticide chlorpyrifos were applied to bare soil in a field with 5% slope and soil and runoff water pesticide concentrations were monitored. In 1997, a rainfall-runoff simulation experiment was conducted on a small sub-plot in order to measure pesticide runoff under reasonable worst-case conditions. Under natural rainfall almost all losses occurred in a large runoff event in 1996 one month after application in which 3% of atrazine and 1% of acetochlor was transported off the field. Propizochlor and chlorpyrifos losses in the same event were much lower: 0.2% and <0.01%, respectively, because of these chemicals' shorter persistence times in near-surface soil. The rainfall simulation produced only trace amounts of losses even though 4.1 cm was applied in 2 hours; the soil was extremely dry and only 0.2 cm runoff occurred containing less than 0.01% of all chemicals applied. The results suggest that intensive use of corn herbicides, which have been found to result in widespread contamination of water resources elsewhere, may be expected to have the same impact in the Balaton watershed depending on the amounts and intensities used in the basin.

Predicted impact of transgenic, herbicidetolerant corn on drinking water quality in vulnerable watersheds of the mid-western USA.

In the intensely farmed corn-growing regions of the mid-western USA, surface waters have often been contaminated by herbicides, principally as a result of rainfall runoff occurring shortly after application of these to corn and other crops. In some vulnerable watersheds, water quality criteria for chronic human exposure through drinking water are occasionally exceeded. We selected three settings representative of vulnerable corn-region watersheds, and used the PRZM-EXAMS model with the Index Reservoir scenario to predict corn herbicide concentrations in the reservoirs as a function of herbicide properties and use pattern, site characteristics and weather in the watersheds. We compared herbicide application scenarios, including broadcast surface pre-plant atrazine and alachlor applications with a glyphosate pre-plant application, scenarios in which losses of herbicides were mitigated by incorporation or banding, and scenarios in which only glyphosate or glufosinate post-emergent herbicides were used with corn genetically modified to be resistant to them. In the absence of drift, in almost all years a single runoff event dominates the input into the reservoir. As a result, annual average pesticide concentrations are highly correlated with annual maximum daily values. The modeled concentrations were generally higher than those derived from monitoring data, even for no-drift model scenarios. Because of their lower post-emergent application rates and greater soil sorptivity, glyphosate and glufosinate loads in runoff were generally one-fifth to one-tenth those of atrazine and alachlor. These model results indicate that the replacement of pre-emergent corn herbicides with the post-emergent herbicides allowed by genetic modification of crops would dramatically reduce herbicide concentrations in vulnerable watersheds. Given the significantly lower chronic mammalian toxicity of these compounds, and their vulnerability to breakdown in the drinking water treatment process, risks to human populations through drinking water would also be reduced.