A simulation procedure for groundwater quality assessments of pesticides

A procedure is described for making regional assessments of pesticide residue loadings and movement in groundwater underneath and downgradient from treated fields. A Monte-Carlo numerical simulation technique is used to generate model parameters for both the unsaturated and saturated zones. Simulations are performed using the Pesticide Root Zone Model linked to a simple groundwater solute transport model.The procedure is useful for evaluating the potential for producing pesticide residues in drinking water wells before actual field applications are made. Appropriate land management options, including restrictions on pesticide application, also can be developed using this procedure.The procedure was used to assess aldicarb levels in northeastern North Carolina groundwater resulting from application of the pesticide to peanuts. Probability density functions for selected soil characteristics were developed using a direct-access soils information data base. Probability density functions for selected groundwater characteristics were developed from available data for the study area. Simulation results indicated that mass fluxes to groundwater exceeded 0.01 and 0.1 kg ha⁻¹ approximately 6.9 and 1.0 percent of the time, respectively. No fluxes exceeded 0.1 kg ha⁻¹ at a distance of 60 m downgradient in any of the cases evaluated.     

Climate change,phenology, and butterfly host plant utilization

Knowledge of how species interactions are influenced by climate warming is paramount to understand current biodiversity changes. We review phenological changes of Swedish butterflies during the latest decades and explore potential climate effects on butterfly–host plant interactions using the Orange tip butterfly Anthocharis cardamines and its host plants as a model system. This butterfly has advanced its appearance dates substantially, and its mean flight date shows a positive correlation with latitude. We show that there is a large latitudinal variation in host use and that butterfly populations select plant individuals based on their flowering phenology. We conclude that A. cardamines is a phenological specialist but a host species generalist. This implies that thermal plasticity for spring development influences host utilization of the butterfly through effects on the phenological matching with its host plants. However, the host utilization strategy of A. cardamines appears to render it resilient to relatively large variation in climate.     

Pesticide distribution in an agricultural environment in Argentina

An assessment of the off-site migration of pesticides from agricultural activity into the environment in the Neuquen River Valley was performed. The aim of this study was to evaluate the distribution of pesticides in several compartments of a small agricultural sub-catchment. Soil, surface water, shallow groundwater and drift deposition were analyzed for pesticide residues. Results showed the presence of some pesticide residues in soil, surface water and shallow groundwater compartments. The highest detection frequencies in water (surface and subsurface) were found for azinphos-methyl and chlorpyrifos (>70%). In terms of concentration, the highest levels were observed in shallow groundwater for azinphos methyl (22.5 μg/L) and carbaryl (45.7 μg/L). In the soil, even before the application period had started, accumulation of residues was present. These residues increased during the period studied. Spray drift during pesticide application was found to be a significant pathway for the migration of pesticide residues in surface water, while leaching and preferential flows were the main transport routes contributing to subsurface contamination.     

Pesticide distribution in an agricultural environment in Argentina

An assessment of the off-site migration of pesticides from agricultural activity into the environment in the Neuquen River Valley was performed. The aim of this study was to evaluate the distribution of pesticides in several compartments of a small agricultural sub-catchment. Soil, surface water, shallow groundwater and drift deposition were analyzed for pesticide residues. Results showed the presence of some pesticide residues in soil, surface water and shallow groundwater compartments. The highest detection frequencies in water (surface and subsurface) were found for azinphos-methyl and chlorpyrifos (>70%). In terms of concentration, the highest levels were observed in shallow groundwater for azinphos methyl (22.5 μg/L) and carbaryl (45.7 μg/L). In the soil, even before the application period had started, accumulation of residues was present. These residues increased during the period studied. Spray drift during pesticide application was found to be a significant pathway for the migration of pesticide residues in surface water, while leaching and preferential flows were the main transport routes contributing to subsurface contamination.     

Plant uptake of pesticides and human health: dynamic modeling of residues in wheat and ingestion intake

Human intake of pesticide residues from consumption of processed food plays an important role for evaluating current agricultural practice. We take advantage of latest developments in crop-specific plant uptake modeling and propose an innovative dynamic model to estimate pesticide residues in the wheat-environment system, dynamiCROP. We used this model to analyze uptake and translocation of pesticides in wheat after foliar spray application and subsequent intake fractions by humans. Based on the evolution of residues in edible parts of harvested wheat we predict that between 22 mg and 2.1 g per kg applied pesticide are taken in by humans via consumption of processed wheat products. Model results were compared with experimentally derived concentrations in wheat ears and with estimated intake via inhalation and ingestion caused by indirect emissions, i.e. the amount lost to the environment during pesticide application. Modeled and measured concentrations in wheat fitted very well and deviate from less than a factor 1.5 for chlorothalonil to a maximum factor 3 for tebuconazole. Main aspects influencing pesticide fate behavior are degradation half-life in plant and time between pesticide application and crop harvest, leading to variations in harvest fraction of at least three orders of magnitude. Food processing may further reduce residues by approximately 63%. Intake fractions from residues in sprayed wheat were up to four orders of magnitude higher than intake fractions estimated from indirect emissions, thereby demonstrating the importance of exposure from consumption of food crops after direct pesticide treatment.     

Aldicarb and carbofuran transport in a Hapludalf influenced by differential antecedent soil water content and irrigation delay

Pesticide use in agroecosystems can adversely impact groundwater quality via chemical leaching through soils. Few studies have investigated the effects of antecedent soil water content (SWC) and timing of initial irrigation (TII) after chemical application on pesticide transport and degradation. The objectives of this study were to investigate the effects of antecedent soil water content (wet vs dry) and timing of initial irrigation (0h Delay vs 24h Delay) on aldicarb [(EZ)-2-methyl-2-(methylthio)propionaldehyde O-methylcarbamoyloxime] and carbofuran [2,3-dihydro-2,2-dimethylbenzofuran-7-yl methylcarbamate] transport and degradation parameters at a field site with Menfro silt loam (fine-silty, mixed, superactive, mesic Typic Hapludalf) soils. Aldicarb and carbofuran were applied to plots near field capacity (wet) or near permanent wilting point (dry). Half of the dry and wet plots received irrigation water immediately after chemical application and the remaining plots were irrigated after a 24h Delay. The transport and degradation parameters were estimated using the method of moments. Statistical significance determined for SWC included averages across TII levels, and significance determined for TII included averages across SWC levels. For the dry treatment, aldicarb was detected 0.10 m deeper (P<0.01) on two of the four sampling dates and carbofuran was detected at least 0.10 m deeper (P<0.05) on all of the sampling dates compared to the wet treatment. Pore water velocity was found to be higher (P<0.10) in the dry vs wet treatments on three of four dates for aldicarb and two of four dates for carbofuran. Retardation coefficients for both pesticides showed similar evidence of reduced values for the dry vs wet treatments. These results indicate deeper pesticide movement in the initially dry treatment. For aldicarb and carbofuran, estimated values of the degradation rate were approximately 40-49% lower in the initially dry plots compared to the initially wet plots, respectively. When the initial irrigation was delayed for 24h, irrespective of antecedent moisture conditions, a 30% reduction in aldicarb degradation occurred. This study illustrates the deeper transport of pesticides and their increased persistence when applied to initially dry soils.     

Linking a one-dimensional pesticide fate model to a three-dimensional groundwater model to simulate pollution risks of shallow and deep groundwater underlying fractured till

The one-dimensional pesticide fate model MACRO was loose-linked to the three-dimensional discrete fracture/matrix diffusion model FRAC3DVS to describe transport of the pesticide mecoprop in a fractured moraine till and local sand aquifer (5-5.5 m depth) overlying a regional limestone aquifer (16 m depth) at Havdrup, Denmark. Alternative approaches to describe the upper boundary in the groundwater model were examined. Field-scale simulations were run to compare a uniform upper boundary condition with a spatially variable upper boundary derived from Monte-Carlo simulations with MACRO. Plot-scale simulations were run to investigate the influence of the temporal resolution of the upper boundary conditions for fluxes in the groundwater model and the effects of different assumptions concerning the macropore/fracture connectivity between the two models. The influence of within-field variability of leaching on simulated mecoprop concentrations in the local aquifer was relatively small. A fully transient simulation with FRAC3DVS gave 20 times larger leaching to the regional aquifer compared to the case with steady-state water flow, assuming full connectivity with respect to macropores/fractures across the boundary between the two models. For fully transient simulations 'disconnecting' the macropores/fractures at the interface between the two models reduced leaching by a factor 24. A fully connected, transient simulation with FRAC3DVS, with spatially uniform upper boundary fluxes derived from a MACRO simulation with 'effective' parameters is therefore recommended for assessing leaching risks to the regional aquifer, at this, and similar sites.     

Experimental variability in characterization of cyfluthrin sorption to soil

To assess the risk of a pesticide to leach to groundwater or to run off to surface water after application, it is necessary to characterize the sorption of the pesticide to soil. For pyrethroids, their hydrophobicity, strong sorption to various materials, and low solubility make it difficult to accurately characterize sorption processes. The objective of this research was to evaluate the variability in cyfluthrin ((RS)-alpha -cyano-4-fluoro-3-phenoxybenzyl (1RS,3RS;1RS,3SR)-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate) sorption to soil as affected by experiment conditions. To minimize cyfluthrin sorption on the walls of glass, silanized-glass, stainless steel, and PTFE centrifuge tubes, cyfluthrin solution was added to aqueous soil slurries or directly to soil, after which it was equilibrated with aqueous solution. Depending on the soil, variation in sorption coefficients, Koc, obtained using different experimental methodologies with one soil can be comparable to the variation in Koc values obtained for soils with different physical and chemical properties using one method. Koc values for cyfluthrin ranged from 56,000 to 300,000 L kg-1. Sorption methodology needs to be evaluated before sorption coefficients are used in predictive transport models.     

Influence of input uncertainty on prediction of within-field pesticide leaching risks

Previous research has suggested that pesticide losses at the field scale can be dominated by a small proportion of the field area. The objective of this study was to investigate whether site-specific applications (i.e. avoiding high-risk areas) at the field scale can contribute to a reduction of pesticide leaching despite uncertainty in the underlying model-based leaching risk map. Using a meta-model of the dual-permeability model MACRO, the annual average pesticide leaching concentrations were estimated for 162 sample sites on a 47 ha field. The procedure was repeated for different scenarios describing different patterns of spatial variation of degradation half-lives and the partition coefficient to soil organic carbon. To account for interpolation uncertainty, maps of predicted pesticide leaching risk were produced by the method of sequential Gaussian simulation. The results of the case study show that larger reductions of predicted leaching were achieved by site-specific application than by that of a comparable uniform dose reduction. Hence, site-specific-applications may be a feasible method to reduce pesticide leaching at the field-scale providing that the model approach gives reasonable estimates of the spatial pattern of pesticide leaching.     

Dynamic modeling of organophosphate pesticide load in surface water in the northern San Joaquin Valley watershed of California

The hydrology, sediment, and pesticide transport components of the Soil and Water Assessment Tool (SWAT) were evaluated on the northern San Joaquin Valley watershed of California. The Nash-Sutcliffe coefficients for monthly stream flow and sediment load ranged from 0.49 to 0.99 over the watershed during the study period of 1992-2005. The calibrated SWAT model was applied to simulate fate and transport processes of two organophosphate pesticides of diazinon and chlorpyrifos at watershed scale. The model generated satisfactory predictions of dissolved pesticide loads relative to the monitoring data. The model also showed great success in capturing spatial patterns of dissolved diazinon and chlorpyrifos loads according to the soil properties and landscape morphology over the large agricultural watershed. This study indicated that curve number was the major factor influencing the hydrology while pesticide fate and transport were mainly affected by surface runoff and pesticide application and in the study area.     

Air and groundwater pollution in an agricultural region of the Turkish Mediterranean coast

Air pollution and groundwater pollution in conjunction with agricultural activity were investigated in Antayla province on the Turkish Mediterranean coast. The air pollution was investigated in terms of gas-phase nitric acid (HNO3), sulfur dioxide (SO2), ammonia (NH3), and particulate matter for a 6-month period in the atmosphere using a "filter pack" system, which was developed and optimized in our laboratory. Ozone was measured by using an automated analyzer. Among all of the gas-phase pollutants, HNO3 had the lowest concentration (0.42 microg x m(-3)) followed by NH3. Agricultural activities seem to be the major source of observed NH3 in the air. The current state of water pollution was investigated in terms of organochlorine and organophosphorus pesticides around the greenhouses, in which mainly tomato, pepper, and eggplant are cultivated. Water samples were collected from 40 points, 28 of which were wells and 12 of which were surface water. The pesticide concentrations in water samples were determined by means of solid-phase extraction (SPE) followed by a gas chromatography (GC)-electron capture detector (ECD)/nitrogen phosphorus detector (NPD) system. In general, surface water samples were more polluted by the pesticides than groundwater samples. The most frequently observed pesticides were chlorpyriphos (57%) and aldrin (79%) in groundwater, and chlorpyriphos (75%), aldrin, and endosulfan sulfate (83%) in surface water samples. The highest concentrations were observed for fenamiphos (394.8 ng/L) and aldrin (68.51 ng/L) in groundwater, and dichlorvos (322.2 ng/L) and endosulfan sulfate (89.5 ng/L) in surface water samples. At least one pesticide had a concentration above the health limit in 38% of all the water samples analyzed.     

Improving the knowledge of pesticide and nitrate transfer processes using age-dating tools (CFC, SF6, H) in a volcanic island (Martinique, French West Indies)

Numerous successful examples of CFC and SF₆ groundwater dating applications were recently published. However the proposed CFC/SF₆ method needs various hydrodynamic parameters that are not always available. In order to predict groundwater-quality trends in areas where the hydrogeological context is poorly known, a dating method using tritium, CFC and SF₆ was successfully implemented in Martinique. Hydrogeological understanding is limited in this volcanic island where groundwater contamination by pesticides and nitrate has been recently proven in various areas. A negative correlation was observed between nitrate concentrations and groundwater ages while pesticide contamination showed a more complex schema. Consequently the presence of old groundwater clearly explained the absence or low pesticide and nitrate concentrations in some areas. However a possible degradation of the water quality is to be feared in the future. In view of the relatively long transfer times and the complexity of the remobilization processes of solutes, the expected effects of any modifications in the use of fertilizers, or of changes in pesticide-use legislation, would take a long time to become apparent.     

Pesticide adsorption on a calcareous soil modified with sewage sludge and quaternary alkyl-ammonium cationic surfactants

BACKGROUND, AIM AND SCOPE: Pesticides are often found in soil as a result of their application to control pests. They can be transported on soil particles to surface waters or they can lixiviate and reach other environmental compartments. Soil modification with amendments, such as sewage sludge, and with surfactants, h been proposed to reduce pesticide environmental fate. METHODS: The sorption of atrazine, methidathion and diazinon using the batch technique has been studied on non-modified soil and soil modified with sewage sludge and cationic surfactants, as well as the effect of their addition on soil properties such as organic carbon (OC) content and exchange cations. RESULTS AND DISCUSSION: The OC content of the surfactant modified soils was the highest with the surfactant with the longest hydrocarbon chain (hexadecyltrimethyl ammonium bromide, HDTMA). The results of the OC content run in parallel with the increase in pesticide retention. When the sorption was n malized to soil OC content, the retention induced by addition of HDTMA was still the highest, which is an indication that the organic matter derived from the organic cations is a more effective medium to retain dissolved contaminants, than organic matter from native soil. The addition of sewage sludge to the soil did only result in a slight increase of the soil CEC and, hence, moderately affected the ability of the cationic surfactant to retain the pesticides. CONCLUSIONS: The addition of cationic surfactants to soil would possibly reduce the movement to groundwater of atrazine, methidathion and diazinon. In the case of HDTMA, the decrease in sorption at high surfactant loadings was very slow, being that the surfactant was able to retain the pesticides at concentration values which clearly exceeded the monolayer coverage. RECOMMENDATIONS AND PERSPECTIVES: Contamination by pesticides, which are present in the soil due to their direct input in this medium or to spills or illegal tipping, may be hindered from migration to groundwater by application of a cationic surfactant.     

The fate of hydrogen peroxide as an oxygen source for bioremediation activities within saturated aquifer systems

In situ bioremediation is an innovative technique for the remediation of contaminated aquifers that involves the use of microorganisms to remediate soils and groundwaters polluted by hazardous substances. During its application, this process may require the addition of nutrients and/or electron acceptors to stimulate appropriate biological activity. Hydrogen peroxide has been commonly used as an oxygen source because of the limited concentrations of oxygen that can be transferred into the groundwater using above-ground aeration followed by reinjection of the oxygenated groundwater into the aquifer or subsurface air sparging of the aquifer. Because of several potential interactions of H2O2 with various aquifer material constituents, its decomposition may be too rapid, making effective introduction of the H2O2 into targeted treatment zones extremely difficult and costly. Therefore, a bench-scale study was conducted to determine the fate of H2O2 within subsurface aquifer environments. The purpose of this investigation was to identify those aquifer constituents, both biotic and abiotic, that are most active in controlling the fate of H2O2. The decomposition rates of H2O2 were determined using both equilibrated water samples and soil slurries. Results showed H2O2 decomposition to be effected by several commonly found inorganic soil components; however, biologically mediated catalytic reactions were determined to be the most substantial.     

Determination of time-dependent partition coefficients for several pesticides using diffusion theory

Diffusion-retarded partitioning of pesticides with aggregated soils results in a time-dependent partition coefficient (Kd') which is different at equilibrium from the partition coefficient derived from conventional 24-h batch studies (Kd) measured on dispersed soil. An experiment was undertaken to determine the importance of Kd' for the prediction of pesticide concentrations in solutions bathing artificial soil aggregates and to determine whether diffusion theory could accurately predict the concentrations. Two clay soils were mixed with polyacrylamide to create artificial aggregates of 0.8, 1.4 and 1.7 cm diameter when dry. After saturation, the aggregates were immersed in solutions containing isoproturon or a mixture of isoproturon, chlorotoluron and triasulfuron. The decline with time of the pesticide concentrations in the bathing solution was monitored and the results were compared with predictions from a diffusion-based model. The effective diffusion coefficients of the compounds were obtained by either fitting the non-linear diffusion model to the data (D(ef)) or by independent calculations based on the properties of the compounds and of the aggregates (D(ec)). The diffusion model was able to predict the temporal variation in pesticide concentrations in the bathing solution reasonably well whether D(ef) or D(ec) values were used. However, equilibrium concentrations in solution were sometimes overestimated due to increased sorption with time at the particle scale. Overall, the ratio between D(ef) and D(ec) ranged from 0.23 to 0.95 which was a reasonable variation when compared to the range of aggregate sizes used in the experiments and of the Kd values of the compounds.     

Effects of sewage sludge amendments on pesticide sorption and leaching through undisturbed Mediterranean soils

The Gharb region in Morocco is an important agricultural zone where soils receive pesticide treatments and organic amendments to increase yields. The groundwater aquifer in the Gharb region is relatively shallow and thus vulnerable. The objective of this work was to study the influence of organic amendments on diuron, cyhalofop-butyl and procymidone leaching through undisturbed soil columns. Two soils were sampled from the Gharb region, a Dehs (sandy soil) and a R'mel (loamy clay soil). Following elution (124.5 mm), the amount of pesticide residues in the leachates of the sandy soil (0.06-0.21 %) was lower than in those of the loamy clay soil (0.20-0.36 %), which was probably due to preferential flow through the loamy clay soil. The amount of procymidone leached through the amended soil columns was greater than the control for the sandy soil only. The organic amendments did not significantly influence diuron and cyhalofop-butyl leaching in either of the soils. The application of organic amendments affected the amounts of dissolved organic matter (DOM) eluted and thus pesticide leaching as a function of soil-type. Nevertheless, in some case, the formation of pesticide-DOM complexes appeared to promote pesticide leaching, thus increasing groundwater contamination risks.     

Fate and distribution of 14C-atrazine in a tropical oxisol

The herbicide atrazine is the most commonly detected pesticide in groundwater world-wide. A new microcosm test-system was used to determine the fate of 14C-atrazine in a Brazilian oxisol. 14C Ring-labelled atrazine was applied in a mixture with the commercial product Gesaprim 500 (Novartis) at a rate of 3 kg ha-1. During two months, about 1% of the initially applied amount was lost by volatilization. The mineralization of the pesticide, measured directly using 14CO2 evolved from the applied pesticide, was between 0.09% and 0.16%, whereas less than 0.2% was leached. The distribution of radioactivity in the soil profile showed that most of the radioactivity remained in the top soil down to a 3 cm depth. The radioactivity in the upper 3 cm of the column was adsorbed perferably in fulvic acid (FA) and human fractions.     

Soil temperature effect in calculating attenuation and retardation factors

The effect of annual variation of daily average soil temperature, at different depths, in calculating pesticides ranking indexes retardation factor and attenuation factor is presented. The retardation factor and attenuation factor are two site-specific pesticide numbers, frequently used as screening indicator indexes for pesticide groundwater contamination potential. Generally, in the calculation of these two factors are not included the soil temperature effect on the parameters involved in its calculation. It is well known that the soil temperature affects the pesticide degradation rate, water-air partition coefficient and water-soil partition coefficient. These three parameters are components of the retardation factor and attenuation factor and contribute to determine the pesticide behavior in the environment. The Arrhenius equation, van't Hoff equation and Clausius-Clapeyron equation are used in this work for estimating the soil temperature effect on the pesticide degradation rate, water-air partition coefficient and soil-water partition coefficient, respectively. These dependence relationships, between results of calculating attenuation and retardation factors and the soil temperature at different depths, can aid to understand the potential pesticide groundwater contamination on different weather conditions. Numerical results will be presented with pesticides atrazine and lindane in a soil profile with 20 degrees C constant temperature, minimum and maximum surface temperatures varying and spreading in the soil profile between -5 and 30 degrees C and between 15 and 45 degrees C.