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The herbicide transport and the groundwater vulnerability to pesticide contamination were studied in the alluvial aquifer of the Rhône River Valley near Martigny (Southwest Switzerland). The low clay and organic matter content of the soil, the intensive agricultural use, and the low depth of the groundwater table, lead to an alleged high vulnerability of the groundwater to contamination. Groundwater is used for irrigation, drinking water supply, and industrial purposes; it is of great economic and ecological importance which makes it particularly interesting to study. The work consists of local scale transport experiments and a regional monitoring of the groundwater over a two year period. At the local scale, two herbicides (atrazine and isoproturon) and a tracer were applied to instrumented field plots (4 m2) in two consecutive years and the transport through the vadose zone was studied in detail. Water flow and solute transport are closely linked to climatic factors. After the application, the pesticides remain at the soil surface as long as no precipitation occurs. Following to the first heavy rainfall, the chemicals are quickly transported through the vadose zone and part of them reaches the groundwater in a short time. During dry periods, the concentrations decrease steadily in the soil profile and the groundwater. After further rainfall, additional concentration peaks are observed in the groundwater, while only small peaks appear near the soil surface. Approximately 2.5 months after the application, the chemical concentration in the soil and in the groundwater has decreased considerably. The experimental results have been used to evaluate a mechanistic deterministic root zone model (HYDRUS-1D). The aim of the simulations was to define the processes involved in pesticide transport and, if possible, to predict the fate of chemicals applied at the soil surface. The MIM (mobile-immobile water) concept was used in order to account for the rapidity of the observed transport. In the study area, the shallow groundwater influences considerably the water conditions in the unsaturated zone; apparently, in such cases the use of a one-dimensional model to simulate the water flow and the chemical transport in the vadose zone is hindered due to difficulties in defining the lower boundary condition. Groundwater flow is typically three-dimensional and therefore, a global (saturated - unsaturated) 3-D model or the coupling of an unsaturated 1-D model to a 3-D saturated model would be more appropriate. Nevertheless, HYDRUS-1D allowed to describe qualitatively the observed results and to confirm the assumption that accelerated flow occurs on the experimental plots. At the regional scale, 13 piezometers were installed in an observation area (400 ha), and the groundwater was regularly analysed for the concentration of 6 herbicides (atrazine, terbutylazine, simazine, deethylatrazine, isoproturon, and diuron). Herbicides were detected in 12 piezometers, sometimes at high concentrations, but during a short period of time (mid May to mid July). Throughout the rest of the year, the concentrations remained below the drinking water limit. The observations are in good agreement with the conclusions of the local experiments (rapid transport, important influence of the climatic conditions, quick decrease of concentration peaks). Furthermore, the groundwater characteristics play an important role for the observation of herbicides. Near the Rhône river, high hydraulic gradients quickly dilute chemicals leaching from the fields above and herbicides coming from more distant fields may also be observed. Near the slope, an inflow of contaminated water from the hill side (vineyards) contributes to the groundwater contamination. Within the plain, high concentrations of herbicides applied to an above located field can temporarily be observed. Contaminations are confined in time and space and different substances are detected from one piezometer to another. This lack of continuity in pesticide concentrations will complicate the prediction of the solutes' fate in the groundwater, and a very precise knowledge of the pesticides use, both in space and time, is required.
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