Jos J. T. I. Boesten

Effects of Soil Heterogeneity on Pesticide Leaching to Groundwater

Pesticide leaching was simulated numerically assuming Freundlich adsorption, first-order transformation and passive plant uptake, taking transient flow, hydrodynamic dispersion, and depth as well as temperature dependence of (bio)chemical parameters into account. The dependency of the leached fraction on sorption and transformation parameters appeared to be in good general agreement with the model developed by Jury et al. (1987). We incorporated spatial variability of )bio)chemical parameters into the piston flow model and showed how spatial variability may be accounted for without having to resort to demanding Monte Carlo techniques. Such spatial variability affects the leached fraction significantly. The data requirement of the simple stochastic model is small and the versatility relatively high. For parameter values often not of prime practical interest for pesticide screening this model fails. Considering transport by convection and dispersion in the semi-infinite domain, this spatial variability can be easily accounted for using parameter ranges for which our original analytical model for spatially variable piston transport failed. In this revised model, hydrodynamic dispersion, preferential flow, and spatial variability of transformation, sorption and soil thickness are dealt with in a similar fashion, while both correlation or the absence of correlation of parameters can be incorporated through an approximation of apparent residence time variance.

A Field Test of Root Zone Water Quality Model—Pesticide and Bromide Behavior

The Root Zone Water Quality Model is a process-based model that integrates physical, chemical and biological processes to simulate the fate and movement of water and agrochemicals over and through the root zone at a representative point in a field with various management practices. The model was evaluated with field data for the movement of water and bromide, and the transformation and transport of cyanazine and metribuzin in the soil profile. The model reasonably simulated soil water and bromide movement. Pesticide persistence was predicted reasonably well with a two-site sorption model that assumes a rate-limited adsorption-desorption process with the additional assumption of negligible degradation of interaggregate-adsorbed pesticides.

Behaviour of metamitron and hydroxy‐chlorothalonil in low‐humic sandy soils

The behaviour of the herbicide metamitron and of the main transformation product, hydroxy-chlorothalonil (HTI), of the fungicide chlorothalonil was studied to assess the risk of leaching from low-humic sandy soil. The adsorption of metamitron corresponded to a Kom value of about 60 dm3 kg−1 (moderate adsorption). The half-life of metamitron in soil at 15 °C was only three days, presumably due to adaptation of the micro-organisms. In the autumn, the residue of metamitron in the soil profiles corresponded to less than 1% of the cumulative dosage. The half-life of chlorothalonil at 15 °C was about 12 days and about 45% of it was transformed to HTI. The adsorption of HTI to the soils corresponded to a Kom value of 260 dm3 kg−1. The incubation study (15 °C) showed the transformation of HTI in the soils to be very slow. The amounts of HTI remaining in the soil profiles in the autumn corresponded to 4 and 16% of the cumulative dosage of chlorothalonil. In winter, the HTI residue decreased by 40% relative to the autumn level. Occasionally, HTI could be detected in the upper ground-water level (at a depth of about 1 m), at an average concentration of 0.1 to 0.2 µg dm−3. © 1999 Society of Chemical Industry

Pesticide Leaching from Agricultural Fields with Ridges and Furrows

In the evaluation of the risk of pesticide leaching to groundwater, the soil surface is usually assumed to be level, although important crops like potato are grown on ridges. A fraction of the water from rainfall and sprinkler irrigation may flow along the soil surface from the ridges to the furrows, thus bringing about an extra load of water and pesticide on the furrow soil. A survey of the literature reveals that surface-runoff from ridges to furrows is a well-known phenomenon but that hardly any data are available on the quantities of water and pesticide involved. On the basis of a field experiment with additional sprinkler irrigation, computer simulations were carried out with the Pesticide Emission Assessment at Regional and Local scales model for separate ridge and furrow systems in a humic sandy potato field. Breakthrough curves of bromide ion (as a tracer for water flow) and carbofuran (as example pesticide) were calculated for 1-m depth in the field. Bromide ion leached comparatively fast from the furrow system, while leaching from the ridge system was slower showing a maximum concentration of about half of that for the furrow system. Carbofuran breakthrough from the furrow system began about a month after application and increased steadily to substantial concentrations. Because the transport time of carbofuran in the ridge soil was much longer, no breakthrough occurred in the growing season. The maximum concentration of carbofuran leaching from the ridge–furrow field was computed to be a factor of six times as high as that computed for the corresponding level field. The study shows that the risk of leaching of pesticides via the furrow soil can be substantially higher than that via the corresponding level field soil.

Rate of transformation of atrazine and bentazone in water-saturated sandy subsoils

When pesticides leach through the soil to the upper groundwater zone, it is important to know whether further transformation occurs before the pumping wells for drinking water are reached. Atrazine and bentazone were incubated (at 10°C) in five water-saturated sandy subsoils (collected at depths between 1·5 and 3·5 m), simulating the conditions in the field. In three subsoils with comparatively low pH and intermediate to high redox potential, atrazine was transformed gradually, to leave 1·9%, 6·2% and 17·5% of the dose after about five years. In one of these subsoils, hydroxy-atrazine was detected; the amount corresponded to half of the dose of atrazine. In one anaerobic subsoil with high pH, the transformation of atrazine was comparatively fast (half-life about 0·15 year). Another anaerobic subsoil, with similar pH and a somewhat higher redox potential, however, showed hardly any transformation. Sterilization of the first anaerobic subsoil had no effect on the rate of transformation. In the course of about five years, bentazone in the first three subsoils was transformed gradually to leave <0·25%, 11% and 25% of the dose. Bentazone transformation in the two subsoils with high pH and low redox potential was very slow, but the presence of oxygen in one of these subsoils speeded up the transformation.

Simulation of movement of pesticides towards drains with a preferential flow version of PEARL.

BACKGROUND As part of the Dutch authorisation procedure for pesticides, an assessment of the effects on aquatic organisms in surface waters adjacent to agricultural fields is required. The peak concentration is considered to be the most important exposure endpoint for the ecotoxicological effect assessment. Macropore flow is an important driver for the peak concentration, so the leaching model PEARL was extended with a macropore module. The new model has two macropore domains: a bypass domain and an internal catchment domain. The model was tested against data from a field leaching study on a cracking clay soil in the Netherlands. RESULTS Most parameters of the model could be obtained from site-specific measurements, pedotransfer functions and general soil structural knowledge; only three macropore-flow-related parameters needed calibration. The flow-related macropore parameters could not be calibrated without using the concentration in drain water. Sequential calibration strategies, in which firstly the water flow model and then the pesticide fate model are calibrated, may therefore be less suitable for preferential flow models. CONCLUSION After calibration, PEARL could simulate well the observed rapid movement towards drains of two pesticides with contrasting sorption and degradation rate properties. The calibrated value for the fraction of the internal catchment domain was high (90%). This means that a large fraction of water entering the macropores infiltrates into the soil matrix, thus reducing the fraction of rapid flow.

Estimating degradation rates in outdoor stagnant water by inverse modelling with TOXSWA: a case study with prosulfocarb

BACKGROUND The regulatory risk assessment of pesticides requires the assessment of exposure of aquatic ecosystems in small surface waters adjacent to agricultural fields. This exposure is predicted using simulation models, for which an important input parameter is the degradation rate in water. In regulatory dossiers, the decline rate in water from outdoor mesocosms is often available, but this rate encompasses more processes than degradation. Therefore, a procedure was designed for estimating the degradation rate in water that was suitable for mesocosm studies with limited datasets, e.g. datasets lacking site-specific sorption coefficients and relevant sediment properties. The procedure, based upon inverse modelling with TOXSWA, has been tested on a dataset for prosulfocarb in stagnant ditches. RESULTS A degradation half-life in the ditch water of 2.9 days (20 °C) was found. This short half-life was to a significant extent accounted for by biodegradation rather than hydrolysis or photolysis. This half-life was considerably shorter than the half-life in the water layer of two laboratory water-sediment system experiments. CONCLUSION The estimation procedure resulted in a unique half-life for the degradation rate in water. Such outdoor mesocosm studies seem to be better suited to assessing the degradation rate in water in ditches than the conventional water-sediment studies.

European scenarios for exposure of soil organisms to pesticides

Standardised exposure scenarios play an important role in European pesticide authorisation procedures (a scenario is a combination of climate, weather and crop data to be used in exposure models). The European Food Safety Authority developed such scenarios for the assessment of exposure of soil organisms to pesticides. Scenarios were needed for both the concentration in total soil and for the concentration in the liquid phase. The goal of the exposure assessment is the 90th percentile of the exposure concentration in the area of agricultural use of a pesticide in each of three regulatory European zones (North, Centre and South). A statistical approach was adopted to find scenarios that are consistent with this exposure goal. Scenario development began with the simulation of the concentration distribution in the entire area of use by means of a simple analytical model. In the subsequent two steps, procedures were applied to account for parameter uncertainty and scenario uncertainty (i.e. the likelihood that a scenario that is derived for one pesticide is not conservative enough for another pesticide). In the final step, the six scenarios were selected by defining their average air temperature, soil organic-matter content and their soil textural class. Organic matter of the selected scenarios decreased in the order North-Centre-South. Because organic matter has a different effect on the concentration in total soil than it has on the concentration in the liquid phase, the concentration in total soil decreased in the order North-Centre-South whereas the concentration in the liquid phase decreased in the opposite order. The concentration differences between the three regulatory zones appeared to be no more than a factor of two. These differences were comparatively small in view of the considerable differences in climate and soil properties between the three zones.

An energetics-based honeybee nectar-foraging model used to assess the potential for landscape-level pesticide exposure dilution

Estimating the exposure of honeybees to pesticides on a landscape scale requires models of their spatial foraging behaviour. For this purpose, we developed a mechanistic, energetics-based model for a single day of nectar foraging in complex landscape mosaics. Net energetic efficiency determined resource patch choice. In one version of the model a single optimal patch was selected each hour. In another version, recruitment of foragers was simulated and several patches could be exploited simultaneously. Resource availability changed during the day due to depletion and/or intrinsic properties of the resource (anthesis). The model accounted for the impact of patch distance and size, resource depletion and replenishment, competition with other nectar foragers, and seasonal and diurnal patterns in availability of nectar-providing crops and wild flowers. From the model we derived simple rules for resource patch selection, e.g., for landscapes with mass-flowering crops only, net energetic efficiency would be proportional to the ratio of the energetic content of the nectar divided by distance to the hive. We also determined maximum distances at which resources like oilseed rape and clover were still energetically attractive. We used the model to assess the potential for pesticide exposure dilution in landscapes of different composition and complexity. Dilution means a lower concentration in nectar arriving at the hive compared to the concentration in nectar at a treated field and can result from foraging effort being diverted away from treated fields. Applying the model for all possible hive locations over a large area, distributions of dilution factors were obtained that were characterised by their 90-percentile value. For an area for which detailed spatial data on crops and off-field semi-natural habitats were available, we tested three landscape management scenarios that were expected to lead to exposure dilution: providing alternative resources than the target crop (oilseed rape) in the form of (i) other untreated crop fields, (ii) flower strips of different widths at field edges (off-crop in-field resources), and (iii) resources on off-field (semi-natural) habitats. For both model versions, significant dilution occurred only when alternative resource patches were equal or more attractive than oilseed rape, nearby and numerous and only in case of flower strips and off-field habitats. On an area-base, flower strips were more than one order of magnitude more effective than off-field habitats, the main reason being that flower strips had an optimal location. The two model versions differed in the predicted number of resource patches exploited over the day, but mainly in landscapes with numerous small resource patches. In landscapes consisting of few large resource patches (crop fields) both versions predicted the use of a small number of patches.

The effect of the runoff size on the pesticide concentration in runoff water and in FOCUS streams simulated by PRZM and TOXSWA

Within the European Union the exposure of aquatic organisms to pesticides is assessed by simulations with the so-called FOCUS Surface Water Scenarios. Runoff plays an important role in these scenarios. As little is known about the effect of runoff size on the exposure, we investigated the effect of runoff size on the concentration in the runoff water and in streams simulated with the PRZM and TOXSWA models for two FOCUS runoff scenarios. For weakly sorbing pesticides (KF,oc<100Lkg-1) the pesticide concentration in the runoff water decreased exponentially with increasing daily runoff size. The runoff size hardly affected the pesticide concentration in the runoff water of strongly sorbing pesticides (KF,oc≥1000Lkg-1). For weakly sorbing pesticides the concentration in the FOCUS stream reached a maximum at runoff sizes of about 0.3 to 1mm. The concentration increased rapidly when the runoff size increased from 0 to 0.1mm and gradually decreased when runoff exceeded 1mm. For strongly sorbing pesticides the occurrence of the maximum concentration in the stream is clearly less pronounced and lies approximately between 1 and 20mm runoff. So, this work indicates that preventing small runoff events (e.g. by vegetated buffer strips) reduces exposure concentrations strongly for weakly sorbing pesticides. A simple metamodel was developed for the ratio between the concentrations in the stream and in the runoff water. This model predicted the ratios simulated by TOXSWA very well and it demonstrated that (in addition to runoff size and concentration in runoff) the size of the pesticide-free base flow and pesticide treatment ratio of the catchment determine the stream concentration to a large extent.