Agricultural diffuse pollution in a chalk aquifer (Trois Fontaines, France): Influence of pesticide properties and hydrodynamic constraints

International audienceThe characterization of the transfer of pesticides to and in groundwater is essential for effective water resource management. Intensive monitoring, from October 1989 to May 2006, of a weakly karstified chalk aquifer system in a 50 km2 agricultural catchment, enabled the characterization of the temporal variability of pesticide concentrations in the groundwater of the main outlet. Atrazine and its metabolite deethylatrazine were quantified 394 and 393 times in 476 samples with concentrations ranging from the quantification limit (0.025 μg L−1) to 5.3 and 1.86 μg L−1, respectively. This common presence, compared to the rare detections of isoproturon (in 108 of 476 samples), the pesticide most widely used in the catchment during at least the past decade, highlighted the significant effect of pesticide properties in the time series of concentrations observed in the groundwater. The use of geochemical tracers (nitrate, chloride) analysed in the groundwater and the hydrodynamic monitoring of the system (discharge, water levels) enabled identification of various infiltration mechanisms governing the functioning of the system. The hydrodynamic study showing that the relative contribution of the infiltration mechanisms varies with time, made it possible to explain major variations observed in the pesticide-concentration time series recorded at the spring

Chiral signatures of herbicides and metabolites concentrations as tools to characterize the hydrodynamic of aquifer

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Use of X-ray diffractometry and analysis of the atomic pair distribution function to study the interactions between smectite and emerging organic pollutants

Aristilde L.; Lanson B.; Charlet L. (2013) Langmuir, 29,International audienceMany emerging pollutants from pharmaceuticals, pesticides or products for domestic or industrial use are found in the environment and pose the problem of achieving good chemical or ecological status of this system. In the environment, these pollutants can interact with different phases that make up soils or sediments, such as organic matter, natural oxyhydroxides, or clay minerals. However, to date there is very little data describing the reaction mechanisms and the nature of the bonds involved in these interactions (Aristilde et al., 2013). In this context, and in order to improve the state of knowledge on the behaviour of emerging pollutants in the environment, we propose to study the adsorption of two organic molecules, sulfamethoxazole (SMX) and metoprolol tartrate (MPT), considered as emerging pollutants onto a Ca-montmorillonite. SMX and MPT are an antibiotic and a cardioselective beta blocker, respectively, and are widely found in soils and aquatic ecosystems, with concentrations up to several micrograms per liter. In this study, SMX and MPT have been in contact with Ca-montmorillonite for 24 hours at pH 6. Different concentrations, varying from0.1 mg/L to 1 mg/L, were studied. The resulting solids were characterized by X-ray powder diffractometry at constant temperature (25°C) and different humidities (from 10 to 90%). Initial results showed differences in the position (interlayer distance) of the 001 reflection of montmorillonite. In the presence of organic molecules and at low humidity, the interlayer distance is greater than that observed in the case of Ca-montmorillonite. This result indicates that the interlayer space has been modified, in particular by the insertion of organic molecules. For relative humidities above 50%, there are no more differences between the samples with and without organic molecules. Due to their small size, organic molecules do not induce significant swelling when the interlayer space contains many water molecules. To complete this study, analyses of the atomic pair distribution function (PDF), were carried out on the starting materials (Ca-montmorillonite, SMX and MPT) as well as on the montmorillonite after having been in contact with the organic molecules. The comparison between the PDFs confirms the adsorption of organic molecules since characteristic peaks of C-H bonds belonging to the CH 3 groups of SMX and MPT are visible on the montmorillonite PDFs after contact with the organic molecules. However, the interatomic distances between C and H seem to be slightly modified indicating a potential reaction mechanism involving these groups. Aristilde L.; Lanson B.; Charlet L. (2013) Langmuir, 29, 4492-4501

Can we infer social preferences from the lab? Evidence from the trust game

We show that a measure of reciprocity derived from the Berg et al. (1995) trust game in a laboratory setting predicts the reciprocal behavior of the same subjects in a real-world situation. By using the Crowne and Marlowe (1960) social desirability scale, we do not find any evidence that a desire to conform to social norms distorts results in the lab, yet we do find evidence that it affects results in the field.

Report on the tracer tests (experimental setup, results and interpretation)

Tracer experiments were performed in the Brévilles test site in order to highlight vertical variations in groundwater fluxes related to vertical variations hydraulic conductivity, to estimate contaminant travel time from several locations in the catchment to the springs and to identify transport processes affecting the fate of solutes in the saturated part of the aquifer. Following a first tracer experiment with uranine and sulforhodamine G in 2003, four tracer injections were performed in November 2005 in different piezometers, using uranine, sulforhodamine B, iodide and lithium. Tracer concentrations were monitored in the injection wells and at the basin outlet (spring and gauging station). Using the FVPDM method, concentration evolutions monitored in the injection wells allowed one to estimate local Darcy fluxes. At the basin outlet, only two tracers were recovered. Analyses of breakthrough curves confirm the stratification of the aquifer with more permeable levels in the lower part. They also suggest the probable occurrence of vertical interactions within the aquifer.AquaTerra - Integrated Modelling of the river-sediment-soil-groundwater system; advanced tools for the management of catchment areas and river basins in the context of global chang

Prédiction des propriétés de rétention en eau des sols d'un bassin versant à l'aide de fonctions de pédotransfert : influence de la densité apparente et de la teneur en éléments grossiers

L'objectif est d'étudier la qualité de l'estimation des propriétés de rétention en eau faite à l'aide de fonctions de pédotransfert (FPT) pour les sols d'un bassin versant de 250 hectares. Ce bassin versant, situé à proximité de Mantes-la-Jolie, au nord-est de Paris, possède des sols limoneux à limoneux-argileux profonds sur la moitié de sa surface, l'autre moitié correspondant à des sols caillouteux. Après une prospection pédologique détaillée, 15 horizons types ont été définis (Tableau 1), puis 22 unités typologiques de sol (UTS) correspondant à la superposition de plusieurs horizons types et enfin 11 unités cartographiques de sols (UCS) regroupant plusieurs UTS (Tableau 2). Les propriétés de rétention en eau des horizons types ont été déterminées au laboratoire pour 8 valeurs de potentiels variant de –10 à –15000 hPa et, en parallèle, estimées à l'aide des FPT proposées par Hall et al. (1977), Jamagne et al. (1977), Rawls et al. (1982), Vereecken (1989), Bastet (1999) et Bruand et al. (2002) pour des valeurs de potentiel appartenant à ce même domaine. L'aptitude des FPT à rendre compte des variations des propriétés de rétention en eau mesurées pour les horizons types est très variable selon les FPT considérées (Tableau 4). Comme d'autres études l'ont déjà montré (Bastet, 1999, Tietje et Tapkenhinrichs, 1993, Wösten et al., 2001), la proximité géographique de la zone d'étude par rapport à celles ayant servi de base aux FPT et la similitude des matériaux parentaux sont des éléments importants à prendre en compte pour apprécier l'aptitude potentielle de FPT à estimer les propriétés de rétention en eau de sol. Une classification par texture, ou par texture et densité apparente, préalablement à l'établissement de FPT, permet d'améliorer la qualité des estimations. La texture et la densité apparente apparaissent donc comme des grandeurs déterminantes pour estimer correctement les propriétés de rétention en eau des horizons de sols étudiés. Toutefois, la densité apparente à l'échelle de l'horizon peut conduire à prendre en compte un volume de pores qui ne contribuent pas à la réserve en eau du sol, car de trop grande taille, et donc conduire certaines FPT à surestimer largement les valeurs de teneurs en eau. Pour les sols qui possèdent des éléments grossiers, dont la présence n'est pas prise en compte par les FPT, une correction des teneurs en eau mesurées et calculées, visant à les exprimer par rapport à la seule fraction fine (< 2 mm) des horizons, ne permet toutefois à aucune FPT de donner des résultats satisfaisants pour les sols caillouteux. Ces sols caillouteux, le plus souvent peu épais, sont ceux pour lesquels la mesure des propriétés de rétention en eau demeure la plus difficile à obtenir, aucune méthodologie adaptée n'étant disponible à l'heure actuelle

Estimating nitrate and pesticide transfer mode within the unsaturated zone of a fluvioglacial aquifer and its implication on spatial and temporal concentration variability

International audienceThe Meyzieu fluvioglacial aquifer of 113 km 2 located at the eastern part of Lyon is intensively exploited and subject to multiple pressures (urban, industrial, agriculture). Nitrate concentrations are quite high while pesticides contamination is low considering the past and today's pressure. A project was initiated in 2011 with the objective of determining the role of the unsaturated zone in the transfer of NO 3 and pesticides from soil to groundwater. Monthly monitoring of major elements, some pesticides, and stable water isotopes is carried out at three sampling points located along the flow lines. Additional information such as hydrogeological functioning, pressure inventory was gathered and additional data from three water sampling campaigns was collected. The temporal variation of NO 3 , metolachlor and metabolites and atrazine and metabolites is quite different at the three monitoring points. At the sampling point located upstream, where the unsaturated zone has a thickness around 40m, the nitrate concentrations are comprised between 20 and 40 mg.l-1 from 2004 to mid-2013. From mid-2013 nitrate concentrations are increasing regularly and are now reaching 70 mg.l-1. This point presents the highest level in atrazine metabolites (DEA) of the area but with concentrations lower than 0.05 µg.l-1 and very low detection of metolachlor or its metabolites. In the centre of the basin, where agriculture pressure is the highest and unsaturated zone of up to 30m in depth, nitrate concentrations are above 50 mg.l-1 with low seasonal variations. Metolachlor is lower than 0.03 µg.l-1 but values of 0,39 µg.l-1 max. of ESA metolachlor (MESA) were reached. Downstream, just before the discharge area, the sampling point shows the lowest and more stable nitrate concentrations (around 40 mg.l-1). The water level in this sector is at less than 20 m deep. Metolachlor have been detected only once while MESA is nearly always detected and can reach 0.24 µg.l-1

Micropollutants and boron isotopes as tracers of the presence of domestic wastewater effluents in surface and groundwaters

International audienc

Fate of TiO2 nanoparticles in the aquatic environment in the presence of anthropogenic compounds

International audienceThe increasing production and use of nanoparticles (NP) in consumer products inevitably lead to ENP emissions into the environment. The physicochemical properties of NP depend on various parameters (e.g. pH, cations, IS). In natural waters, the stability of NP can vary as a function of a sum of these parameters and occurs by one of the numerous scenarios. In particular, the presence of anthropogenic organic molecules (AOM) can change the NP fate. Also, the presence of NP may affect the organic pollutants (fate and toxicity). The main objective of the work was to study the aggregation of TiO2 NP (pure hydrophilic 100 % rutile and pure hydrophilic 100 % anatase, 5−30 nm) in the presence of the most frequently occur and representative pesticides (glyphosate, AMPA, 2.4D) in natural waters considering lab experiments under relevant aqueous conditions (pH, ionic strength, presence and concentrations of mono- and bivalent cations). The presence of pesticides affected TiO2 NP homoaggregation in solutions (IS=10-3M - 10-2M) with pH values below the NP point of zero charge (PZC) for the anatase NPs (pH=6.5) and with pH values above the NP PZC for the rutile NP (pH=4.5). No changes in NP aggregation were observed in very low (IS=10-4M) or very high (IS= 10-1M) ionic strength solutions. The presence of the pesticides caused a significant modification of the NP surface charge (zeta potential) over a large range of salt concentrations (IS=10-4M - 10-1M). Compared to mono-valent cations (Na+), bi-valent cations (Ca2+) favor an increase in zeta potential of NP (anatase and rutile) at pH 8. There is no significant difference between at pH 5. Finally, these results demonstrated that, among the studied AOMs, glyphosate (with 4 pKa-s from 0.8 to 11) affects NP aggregation/stabilization in a wider range of physicochemical conditions. Overall, these results will aid in the evaluation of potential environmental risks posed by engineered NP in the aquatic environments exposed to pesticide load