Transfert de polluants organiques et inorganiques dans les hydrosystèmes en période de crue : interactions avec les matières en suspension et la matière organique

Le transfert des polluants organiques et inorganiques dans les hydrosystèmes est très documenté mais rares sont les études qui s'intéressent à ces transferts en période de crue et dans des situations de multi pollutions. Cette thèse s'inscrit dans ces problématiques-là. Sachant que les flux les plus importants de polluants sont exportés durant les épisodes de crue, nous avons effectué un suivi rigoureux de la crue de mai 2010 sur le bassin versant (BV) de la Save (1110 km2, sud ouest de la France). Un échantillonnage intensif permet de décrire avec précision la réponse du cours d'eau aux fortes précipitations sur le BV. Les principaux paramètres contrôlant le transfert des polluants (carbone organique dissous (COD) et particulaire (COP) et matières en suspension (MES)) sont plus concentrés en crue qu'en étiage. Ces paramètres, ainsi que les polluants voient, pour la plupart, leur teneur augmenter avec le débit. Une séparation des composantes de l'écoulement fluvial par découpage de l'hydrogramme de crue montre que les polluants sont majoritairement apportés dans l'écoulement de surface adsorbés aux MES pour les moins solubles et dans l'écoulement de subsurface liés au COD pour les plus solubles. Au niveau des MES, le polluant peut se lier à différentes fractions (matières organiques, argiles et oxydes). Afin de mieux comprendre les liens établis entre un polluant et les MES au cours de son transfert, nous nous sommes focalisé dans le cadre projet CRUMED (EC2CO-INSU/CNRS), sur la dynamique du Cu dans le BV de la Baillaury (18,2 km2) à Banyuls sur Mer dans les Pyrénées-Orientales. Sur ce BV viticole méditerranéen, la bouillie bordelaise (sulfate de cuivre) est appliquée sur les parcelles depuis des siècles. Ces traitements ont entraîné un enrichissement en Cu, par rapport à la roche mère locale, des sols, des sédiments de fond et des MES. La contribution anthropique à cet enrichissement est supérieure à 60%. Une extraction chimique séquentielle montre que le Cu dans les échantillons peu contaminés est surtout dans la fraction résiduelle stable alors que dans les échantillons contaminés, il est dans les fractions non résiduelles, principalement lié aux oxydes de fer. La signature isotopique des fractions obtenues montrent que le Cu transporté dans la solution et celui lié à la matière organique ne subissent pas de fractionnement. La combinaison de ces 2 approches permet de mieux comprendre la distribution et la mobilité de l'élément dans l'environnement. Cependant, dans les milieux anthropisés, un polluant est rarement seul et la présence d'autres polluants peut influencer son adsorption. Afin de mettre en évidence l'existence de ces influences mutuelles, nous avons mené une expérimentation sur l'adsorption des polluants organiques et inorganiques sur des MES issues de la Save en crue. On montre que l'adsorption des polluants seuls dans le milieu est, dans la plupart des cas, différente de celle en présence d'autres polluants. Les éléments traces métalliques (ETM) étudiés (Cu et Cd) sont peu sensibles à la présence de polluants organiques étudiés (alachlore et aclonifène), alors que les pesticides s'adsorbent plus (alachlore) ou moins (aclonifène) en présence d'autres polluants (ETM ou pesticides). L'ordre de la présence dans le milieu modifie aussi le taux d'adsorption. L'influence se ferait soit par compétition pour les mêmes sites de fixation soit par formation de complexes entre les polluants modifiant leur solubilité. Ces résultats originaux ouvrent de nouvelles perspectives et suscitent de nouvelles expérimentations pour mieux caractériser les liaisons polluants-MES et les relations entre les différents polluants lors de l'adsorption sur les MES.The mechanisms involved in the transfer of organic and inorganic pollutants to streams in agricultural watersheds are largely studied. However, few studies concern storm events responsible for the transportation of large quantities of pollutants to the outlet and they rarely take into account a multi-pollution dynamic. A heavy monitoring was therefore conducted during the storm event of May 2010 at the outlet of the Save river (1110 Km2) in the south west of France. The majority of pollutants and their controlling factors (dissolved and particulate organic carbon (DOC and POC) and suspended particulate matter (SPM)) are more concentrated during storm flow than base flow and their concentration increases with stream water discharge. Pollutants are also more concentrated during these events. Hydrograph separations showed that pollutants are primarily transported in the surface runoff adsorbed onto SPM when they have a low solubility (hydrophobic) and in the subsurface runoff linked to DOC when they are soluble. Different kinds of chemical bonds can exist between pollutants and the different SPM fractions (organic matter, clay and oxides). In order to investigate these bonds, we studied in particular Cu dynamic in the small wine growing catchment of Baillaury (18.2 Km2), close to Banyuls sur Mer (Eastern Pyrénées), within the framework of the CRUMED project (EC2CO-INSU/CNRS). This Mediterranean type-flow regime stream is mostly cultivated with vineyards and has been treated with Bordeaux mixture for centuries. Moderate to significant enrichments of soils at different depth, river bottom sediments and suspended matters were revealed. Anthropogenic contribution to this enrichment is estimated between 50 and 85 % in all samples showing that the Cu present in the river is mainly due to agricultural practices. Sequential chemical extractions SCE) allow us to determine Cu distribution in the different residual and non-residual fractions (exchangeable, acido-soluble, Mn and Fe oxides, organic matter), showing that anthropogenic Cu is mainly adsorbed onto iron oxides. The isotopic Cu composition measured in each fraction shows that Cu transported in solution and adsorbed onto organic matter seems to be associated without any fractioning. Gross samples have signatures similar to the bedrock and so studying the detailed SCE fractions is essential. Combining SCE and isotopic signatures is a powerful tool to understand Cu distribution and transfer in the environment. However, in the environment, a pollutant is rarely alone and other pollutants can influence its fate. Therefore, in order to investigate the influence of the presence of other pollutants on a pollutant's adsorption, organic (two pesticides: alachlore and aclonifen) and inorganic (two heavy metals: Cu and Cd) pollutants adsorption on natural SPM (collected in the Save river during the flood) were studied. Most studied pollutants were influenced by the presence of one or more other pollutants in the water, trace metals to a lesser extent than pesticides. The order of presence in the water also influences the adsorption rate of the pollutant onto SPM. The mutual influence can be due to competition for the same adsorption sites or to the creation of complexes between pollutants. These complexes can modify the adsorption capacities of each pollutant. These original results obtained in this work open up new perspectives and req

Elemental and isotopic composition of river water during a flood event in agricultural watershed: insight of sources and pathways of water and terrestrial derived matter

Flood event in agricultural watershed represents 64% of water discharge but up to 71% of dissolved organic carbon and 94 of total suspended matter export. It therefore constitutes a key period to assess change in surface water contamination and quality. While during base flow conditions most of river discharge is supported by groundwater input, during storm period surface and subsurface runoffs contribute to river flow. Integration of water pathway complexity and spatial heterogeneity of contaminant inputs in the watershed need to be assessed by biogeochemical proxy measured at watershed outlet in the main river channel

New insights on Cu origin and fate from combined chemical extraction and ᵟ⁶⁵Cu isotopic composition: Application to Cu transfers in a Mediterranean vineyard catchment

Repeated use of Cu based fungicides (Bordeaux mixture: Ca(OH)2+CuSO4) to control vine downy hasled to signi!cant increase of Cu in vineyard soils. In Mediterranean catchments, brief and intense flood events can multiply stream discharge by up to 10 and are responsible for important soil leaching and therefore for high "uxes of Cu exported at the outlet of the catchment. In order to assess the origin and fate of Cu measured in the Baillaury catchment (South of France, combined sequential extraction (SCE) and isotopic Cu compositions (δ65Cu) approaches are proposed in this study

Origin and fate of copper in a small Mediterranean vineyard catchment: New insights from combined chemical extraction and δ65Cu isotopic composition

For centuries, many Mediterranean catchments were covered with vineyards in which copper was widely applied to protect grapevines against fungus. In the Mediterranean-type flow regime, brief and intense flood events increase the stream water discharge by up to 10 times and cause soil leaching and storm runoff. Because vineyards are primarily cultivated on steep slopes, high Cu fluxes are discharged by surface water runoff into the rivers. The purpose of this work was to investigate the riverine behavior and transport of anthropogenic Cu by coupling a sequential chemical extraction (SCE) procedure, used to determine Cu partitioning between residual and non-residual fractions, with δ65Cu isotopic measurements in each fraction. In the Baillaury catchment, France, we sampled soils (cultivated and abandoned), river bed sediments (BS), suspended particulate matter (SPM), and river water during the flash flood event of February 2009. Copper partitioning using SCE show that most of Cu in abandoned vineyard soil was in the residual phase (>60%) whereas in cultivated soil, BS and SPM, Cu was mostly (>25%) in non-residual fractions, mainly adsorbed onto iron oxide fractions. A small fraction of Cu was associated with organic matter (5 to 10%). Calculated enrichment factors (EF) are higher than 2 and the anthropogenic contribution was estimated between 50 to 85%. Values for δ65Cu in bulk samples were similar to bedrock therefore; δ65Cu on SCE fractions of superficial soils and SPM allowed for discrimination between Cu origin and distribution. Copper in residual fractions was of natural mineral origin (δ65Cu close to local bedrock, +0.07‰). Copper in water soluble fraction of SPM (δ65Cu = +0.26‰) was similar to dissolved river Cu (δ65Cu = +0.31‰). Copper from fungicide treatment (δ65Cu = −0.35‰) was bound to organic matter (δ65Cu = −0.20‰) without or with slight isotopic fractioning. A preferential adsorption of 65Cu onto iron oxides (δ65Cu = +0.5‰) is shown

High-frequency monitoring of surface water quality at the outlet of the Ibrahim River (Lebanon): A multivariate assessment

Surface water quality monitoring is essential to evaluate the quality of a water resource. The current study assesses the quality of the Ibrahim River, one of the main Lebanese rivers, exposed to considerable human activities. 285 samples were collected at the outlet of the river, between May 2016 and July 2017, covering one hydrological year. Twenty-three physico-chemical parameters (flow, pH, temperature, electrical conductivity, turbidity, total suspended solids, total dissolved solids, dissolved oxygen, dissolved organic carbon, biochemical oxygen demand, chemical oxygen demand, chemical oxygen demand/biochemical oxygen demand, specific ultraviolet absorbance, dissolved cations (Na+, K+, Ca2+, Mg2+), total alkalinity, dissolved anions (Cl−, NO3 −, NO2 −, PO4 3− and SO4 2−)) and five microbiological tests were assessed (total germs, total coliforms, fecal coliforms, Escherichia coli and Enterococcus). A Principal Component Analysis (PCA) was applied for data analysis. The first component showed high levels of anthropogenic characteristics mainly due to organic and bacteriological parameters, differentiating low and high river discharges (explaining around 35% of the total variance). The second component was mainly influenced by mineral variables showing a clear annual discrimination (explaining about 17% of the total variance). Moreover, this study led to variables reduction from twenty-eight to ten. The final shortlisted parameters are Q, pH, EC, NO3 −, total coliforms, fecal coliforms, BOD5, K+, TA and Cl−. A new PCA performed with the reduced matrix validated this selection. The water quality index (WQI) was then calculated in this study, using the shortlisted parameters characterizing the basin, excluding the flow since it cannot be considered as a quality indicator. Thus, the water was evaluated as « medium » to « good » with values ranging from 63.1 (August 2016) to 73.1 (November and December 2016) with an average of 69.0 ± 1.9. The proposed WQI should be further tested for monitoring practices in the Ibrahim River basin or other similar basins of the region

Trace Element and Pesticide Dynamics During a Flood Event in the Save Agricultural Watershed: Soil-River Transfer Pathways and Controlling Factors

Agricultural practices are the main source of water contamination in rural areas. Rainfall events, and subsequently, soil leaching and storm runoff are mainly controlling the transfer of pollutants from diffuse sources in watersheds during floods. These periods are also very important to better understand their dynamics, particularly their different soil-river transfer pathways (surface runoff SR, subsurface runoff SSR, and groundwater flow GF). This study focuses on riverine transfers of both pesticides and trace elements. High-resolution monitoring of water discharge and water sampling were performed during a flood event that occured in May 2010 in an agricultural catchment of SWFrance. Chemical composition of major and trace elements, silica, alkalinity, pH and conductivity, DOC and POC, TSM, and commonly used pesticides were analyzed with a high sampling frequency. The different stream flow components (SR, SSR, and GF) were assessed using two independent hydrograph separation methods: a hydrological approach based on Maillet’s formula (1905) for the recession period and a chemical approach based on physico-chemical tracers, TSM for SR and PO43− for GF. Both methods exhibited important contributions of SR (33 %) and SSR (40 %) to the total riverine pollutant transfers. The contribution of different components was also visible using concentration-discharge relationships which exhibited hysteresis phenomenon between the rising and the falling limbs of the hydrograph. Higher concentrations during the rising period(clockwise hysteresis) were characteristic of pollutants mainly exported by SR (trifluralin, Cd). Anticlockwise hysteresis with higher concentration during the recession period showed pollutants mainly exported by SSR (metolachlor, Cu). Moreover, significant relationships were highlighted between the controlling factors (DOC,POC, and TSM) and SR, SSR, and GF contributions:DOC and the complexed pollutants were highly correlated to SSR while POC, TSM, and the adsorbed pollutants were linked to SR. During the flood, Kd of most pollutants increased, particularly at the beginning, and therefore,future studies should investigate their availability to living organisms and thus their toxicity. An additional characteristic equation between Kd and Kow of the different pesticides was proposed to help future management, modelling,and estimation of pollutant transfers during floods

Elemental and isotopic composition of river water during a flood event in agricultural watershed: insight of sources and pathways of water and terrestrial derived matter

International audienceFlood event in agricultural watershed represents 64% of water discharge but up to 71% of dissolved organic carbon and 94 of total suspended matter export. It therefore constitutes a key period to assess change in surface water contamination and quality. While during base flow conditions most of river discharge is supported by groundwater input, during storm period surface and subsurface runoffs contribute to river flow. Integration of water pathway complexity and spatial heterogeneity of contaminant inputs in the watershed need to be assessed by biogeochemical proxy measured at watershed outlet in the main river channel

New insights on Cu origin and fate from combined chemical extraction and ᵟ⁶⁵Cu isotopic composition: Application to Cu transfers in a Mediterranean vineyard catchment

International audienceRepeated use of Cu based fungicides (Bordeaux mixture: Ca(OH)2+CuSO4) to control vine downy hasled to signi!cant increase of Cu in vineyard soils. In Mediterranean catchments, brief and intense flood events can multiply stream discharge by up to 10 and are responsible for important soil leaching and therefore for high "uxes of Cu exported at the outlet of the catchment. In order to assess the origin and fate of Cu measured in the Baillaury catchment (South of France, combined sequential extraction (SCE) and isotopic Cu compositions (δ65Cu) approaches are proposed in this study