Les concentrations élevées en pesticides dans les eaux de surface drainant des bassins versants agricoles sont devenues une préoccupation majeure en Europe depuis une cinquantaine d'années. Les pesticides sont transférés dans l'environnement par différentes voies (le ruissellement de surface et de sub-surface, le flux de nappe), soit en solution soit adsorbés aux particules de sol en suspension dans l'eau. Les eaux de ruissellement et de percolation entraînent avec elles des charges de contaminants dont les concentrations en solution peuvent s'avérer toxiques pour la faune et la flore aquatique et rendre l'eau impropre à la consommation humaine si le réseau de drainage est une source de captage pour l'alimentation en eau potable. Les crues constituent donc des événements hydrologiques de première importance dans la contamination des eaux continentales par les pesticides. Les objectifs de cette thèse ont été de (1) caractériser, à l'aide d'un modèle agro-hydrologique, la dynamique des transferts de pesticides à l'échelle du bassin versant dans une région agricole, notamment en période de crue ; (2) identifier les facteurs de contrôle du transfert de pesticides et (3) améliorer, le cas échéant, les équations formalisées dans le modèle. Deux approches ont été menées de front afin de répondre aux questions posées : l'analyse de données mesurées et modélisées sur le bassin versant agricole de la Save (sud-ouest de la France). Une étude de faisabilité réalisée en préliminaire a montré que le modèle Soil and Water Assessment Tool (SWAT - Arnold et al., 1998) était adapté à la modélisation du transfert de pesticides, dans les phases dissoute et particulaire, à l'échelle du bassin versant. L'hydrologie et les concentrations à l'exutoire des phases dissoute et particulaire (respectivement les nitrates et les matières en suspension) ont été calibrées. Les voies privilégiées de transfert des pesticides en fonction des conditions hydrologiques ont été identifiées. La modélisation a ensuite été mise en œuvre avec des itinéraires techniques plus détaillés en entrée du modèle et des mesures sub-journalières de pesticides en crue. Les différentes voies de transfert des pesticides dans les deux phases, ainsi que leurs facteurs de contrôle environnementaux, ont été étudiés. Deux facteurs de contrôle, respectivement dépendant des pratiques agricoles (la date d'application des pesticides, qui est un facteur anthropique) et intrinsèque aux molécules de pesticides (le coefficient Kd de partition entre phases dissoute et particulaire, qui est un facteur physico-chimique) ont été abordés plus en détail. Le rôle de la typologie du bassin versant sur les transferts est discuté. Des cartes de risque de contamination des eaux de surface par les pesticides sont présentées pour le bassin de la Save. Dans la perspective d'améliorer le formalisme des modèles de transfert des pesticides, une équation qui relie le coefficient Kd au coefficient de distribution octanol/eau Kow et à la concentration en matières en suspension a été proposée. / Rising pesticide levels in streams draining intensively managed agricultural land has become a widespread problem throughout Europe in recent decades. Pesticides are transferred into the environment through various pathways (surface and sub-surface runoff, groundwater return flow), either in solution or sorbed onto particles. Runoff and percolating water carry contaminants loads which concentrations in solution may be harmful to terrestrial and aquatic ecosystems rendering water unfit to human consumption if the draining network is a source for drinking water. Floods are hydrological events of major importance in continental waters contamination by pesticides. The objectives of this PhD thesis were (1) to characterise pesticides transfer dynamics at catchment scale in an agricultural area during floods; (2) to identify the factors controlling pesticides transfer and (3) to improve modelling by changing formalism with more suitable equations. Two approaches were set up: analysing both measured and simulated data sets, stemming from the River Save catchment (south-western France). A preliminary feasibility study showed that the Soil and Water Assessment Tool (SWAT - Arnold et al., 1998) was adapted for pesticides transfer modelling in both dissolved and sorbed phases, at catchment scale. Water discharge, dissolved and sorbed phases (respectively nitrate and suspended sediments) were calibrated. Pesticides transfer preferred pathways depending on hydrological conditions were identified. Modelling was then carried on more detailed management practices as input and on sub-daily pesticides concentration measurements during flood events. The various transfer pathways in both phases together with the environmental controlling factors were assessed. At last, two controlling factors, respectively depending on management practices (application date, an anthropogenic factor) and on an intrinsic pesticide molecule property (the partition coefficient Kd which is a physico-chemical factor) were studied. The role of catchment typology was discussed. Surface water contamination risk maps were drawn on Save catchment. In order to improve the formalism of pesticide transfer models, an equation was proposed that relates Kd to the octanol/water partition coefficient Kow and to suspended matter concentration.

Persistent organic pollutants (POPs) are hydrophobic substances that readily sorb to organic matter in particles and colloids instead of being freely dissolved in the water phase. This sorption affects the bio­availability and environmental transport of the POPs. The major part of this thesis concerns the role of sediments as secondary sources of POPs. As the primary emissions decrease, contaminated sediments where POPs have accumulated can become the main source of contamination. If the contaminated sediment by time becomes covered with cleaner layers, the POPs are buried and no longer in contact with the aquatic environment. Experiments in this thesis showed, however, that new invading species can alter the sediment-water dynamics as a result of their bioturbation, i.e. mixing of sediment particles and pore-water. Marenzelleria spp., invading species in the Baltic Sea that burrow deeper than native species, were found to increase the remobilization of buried contaminants. The sediment-to-water flux was inversely related to the burial depth (2-10 cm) of the POP congeners (polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers) and also inversely related to the hydrophobicity of the congener. The flux was therefore most pronounced for less hydrophobic contaminants, which was linked to the bioirrigating behaviour of these species. Marenzelleria spp. also accumulated the buried POPs and increased concentrations in surface sedi­ment. Contaminants previously considered buried at a ’safe’ depth can thus be remobilized as a result of the invasion of Marenzelleria spp. in the Baltic Sea. One method to decrease the remobilization of contaminants from sediments is ’capping’, i.e. a layer of clean material is placed as a cap on the sediment. By amending the cap with active materials, which sequester the POPs and decrease their availability, thinner layers can be used (’active capping’ or ’thin-layer capping’). Results from an experiment with thin-layer capping using different active materials (activated carbon (AC) and kraft lignin) showed that both the sediment-to-water flux and the bioaccumulation by benthic species of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), hexachlorobenzene (HCB) and octachlorostyrene (OCS) decreased with increased thick­ness of the cap layer (0.5-5 cm). Amendments with active materials further increased the cap efficiency. AC was more efficient than kraft lignin, and a 3 cm cap with 3.3% AC reduced the flux and bioaccumulation with ~90%. The reduction of the sediment-to-water flux was inversely related to the hydrophobicity of the POP, and reductions in the flux had similar magnitudes as reductions in the concentration in deep-burrowing polychaetes, demonstrating the importance of bioturbation for sediment-to-water transport. In a one-year study on the levels of PCDD/Fs, PCBs, and HCB in a coastal area of the Baltic Sea, the correlations between the POP levels and the levels of particles and organic carbon in the water were found to differ for POPs of different structure and hydrophobicity. The levels of PCDD/Fs decreased to one third in May, which could be related to the increased sedimentation, i.e. water-to-sediment transport, during spring bloom.