Tracking selenium in the Chalk aquifer of northern France: Sr isotope constraints

International audienceGroundwater at the southern and eastern edges of France's Paris Basin has a selenium content that at times exceeds the European Framework Directive's drinking-water limit value of 10 µg/L. To better understand the dynamics of the Chalk groundwater being tapped to supply the city of Lille and the Se origins, we used a combination of geochemical and isotopic tools. Strontium isotopes, coupled with Ca/Sr, Mg/Sr and Se/Sr ratios, were used to identify the main groundwater bodies and their mixings, with the Mg/Sr ratio constraining a ternary system. Groundwater in the agricultural aquifer-recharge zone represents a first end-member and displays the youngest water ages of the catchment along with the highest strontium isotopic signature (0.7084) and low Se contents. Anaerobic groundwater constitutes a second major end-member affected by water-rock interactions over a long residence time, with the lowest strontium isotopic signature (0.7079) and the lowest Se content, its low SF6 content confirming the contribution of old water. Se-rich groundwater containing up to 30 µg/L of Se represents a third major end-member, with an intermediate Sr isotopic ratio, and is mainly constrained by the clayey Se-rich formation overlying the Chalk aquifer. The spatial and temporal Se variability in the groundwater is clearly linked to the presence of this formation identified as Tertiary and also to the hydrological conditions; saturation of the Se-rich clays by oxygenated groundwater enhances Se mobility and also Sr adsorption onto the clays. This multi-tool study including Sr isotopes successfully identified the Se origins in the aquifer and has led to a better understanding of the regional mixing and processes affecting the Chalk groundwater

Multi isotopic tools to understand selenium origins in groundwaters of the Chalk aquifer in Northern France

International audienceFour field wells exploiting the Chalk aquifer supply Lille city in water. The little catchment area is submitted to quantitative and qualitative pressure from industrial, urban and agriculture origins. Selenium (Se) concentrations are often higher than EU standards (0.12 µmol.L-1) for potable drinking water and can reach 0.4 μmol.L-1 leading to exploitation restrictions. An integrated study was settled to determine the water sources and dynamics of elements, with a focus on Se, with the goal of managing both water quality and quantity. After a large chemical characterisation of the system, a monthly sampling campaign was held in 2012 in four wells and in the close Deûle channel. In situ physical and chemical parameters, chemical analysis of major and trace elements with a special focus on redox-sensitive elements including SeIV, SeVI, FeII, stable water isotopes (δ18O, δ2H) and δ34S and δ18O of sulphates measures were undertaken. The chemical composition of solids sampled at various depths at vicinity of the four wells was analysed. Se concentrations in groundwaters and in the solid phase vary significantly. In the northern part of the Ansereuilles north of the Deûle channel, where the highest Se concentrations in solids was found in a 13 m alluvial clay deposit above the chalk, a first main type of waters can be defined with the variable and locally highest Se concentrations (0.19 to 0.4 µmol.L-1), relatively high and stable sulphate concentrations (2.5 µmol/L), no nitrates, dissolved Fe and Mn, negative δ34S (around -20 ‰) and δ18O typical of evaporated waters. A second main type of waters can be described at Houplin, south of the Deûle channel, where the geological profile show less than 1 mg/kg of Se, with intermediate Se concentrations (0.1 to 0.2 µmol/L), variable nitrate concentrations (0.4 to 1.2 mmol/L), not quantified dissolved Fe and Mn, sulphate concentrations close to 1.5 mmol/L, variable negative δ34S (-8 to -24 ‰) and δ18O in the same trend as previously described. Groundwaters from the two other wells have characteristics relatively close to the Houplin's type. All sampled groundwaters show a variation of the stable isotopes signatures in winter indicating the contribution of evaporated of waters from a different source. Given the negative δ34S, the role of redox processes, and especially of pyrite oxidation, is expected. These two types of groundwaters can be linked to the two local hydrogeological entities of the Chalk aquifer; in the northern edge of the Deûle, the chalk groundwater flux is rather limited under the influence of the Louvil clays. On the contrary, on the southern edge of the Deûle where Houplin and the two other wells are located, the flux gradient is high and the vulnerable groundwaters drain a large cultivated, industrial and urban area. Se may at least have two origins: the lithology in the Ansereuilles can be a clear source of Se whereas different influences can be suggested for the Houplin site in connexion with the hydrogeological and anthropogenic context

Tracking selenium behaviour in chalk aquifer (northern France): Sr and 34S-sulphates isotopes constraints.

International audienceGroundwaters in parts of the Paris Basin (France) are facing increasing selenium (Se) contents that can exceed the drinking water limit of 10 µg/L according to the European Framework Directive in the field of water policy (2000/60/EC). To better understand the groundwater origins and the selenium dynamics, the water chemistry of the Chalk aquifer supplying drinkable water to Lille city was studied. This area is submitted to quantitative and qualitative pressure from industrial, urban and agriculture origins. An integrated study was settled to determine the water sources and dynamics of elements, with a focus on Se. After a large chemical characterisation of the groundwater chemistry in the four field wells, a monthly monitoring was held in four wells and in the Deûle channel. Chemical analysis of major and trace elements, stable isotopes (δ18O, δ2H), strontium isotopes, and δ34S and δ18O of sulphates were realised. The chemical composition of solids sampled at various depths at vicinity of the four wells was also analysed. The specific geochemical signature of groundwater as revealed by Sr isotopes, in addition to element concentrations ratios like Mg/Sr and Se/Sr, highlighted mixture of three main groundwaters bodies: (1) the upstream groundwaters in the recharge area with the most radiogenic 87Sr/86Sr isotopic signature; (2) the confined groundwaters with high Sr concentrations due to water-rock interactions and the lowest 87Sr/86Sr isotopic signature close to the one of the chalk in Paris and London basins; (3) the Se-rich formations of Tertiary and Quaternary. The contents of Se, mainly present as SeVI (and locally as SeIV), displayed spatial and temporal disparities that can be explained by geological and hydrogeological conditions. Se-rich clayed sediments originating from the dismantling of Se-rich tertiary formations (i.e. Ypresian) overlay the chalk formation and can be found in saturated conditions depending of the water table level. Oxidation of Se0, Se-pyrite and Se linked to organic matters happens according to two pathways. The first one is oxidation of Se species present in the reductive clayed sediments by oxidizing groundwaters during periods of high piezometric levels. The decrease of the piezometric level induces a decrease of the Se contents in groundwaters. Negative δ34S (0 to -28 ‰) coherent with pyrite oxidation are observed in groundwater. The second one is linked to the infiltration of nitrate-rich recharge waters through quaternary loess which also contain Se. In this case, δ34S of groundwaters are slightly positive and close to the signature of fertilizers. Denitrification by pyrite or Se0 oxidation plays a great role in enhancing Se mobility in a very reactive system. To limit the Se content in groundwaters, a precise water management is needed, e.g. mainly maintaining low piezometric levels in the chalk aquifer or avoiding mixings between contaminated wells, together with a precise knowledge of the geology of the quaternary clayed sediments