Abstract: The Roussillon sedimentary Basin (South France) is a complex multi-layered aquifer, close to the Mediterranean Sea facing seasonally increases of water abstraction and salinization issues. We report geochemical and isotopic vertical variability in this aquifer using groundwater sampled with a Westbay System® at two coastal monitoring sites: Barcarès and Canet. The Westbay sampling allows pointing out and explaining the variation of water quality along vertical profiles, both in productive layers and in the less permeable ones where most of the chemical processes are susceptible to take place. The aquifer layers are not equally impacted by salinization, with electrical conductivity ranging from 460 to 43,000μS·cm−1. The δ2H–δ18O signatures show mixing between seawater and freshwater components with long water residence time as evidenced by the lack of contribution from modern water using 3H, 14C and CFCs/SF6. S(SO4) isotopes also evidence seawater contribution but some signatures can be related to oxidation of pyrite and/or organically bounded S. In the upper layers 87Sr/86Sr ratios are close to that of seawater and then increase with depth, reflecting water–rock interaction with argillaceous formations while punctual low values reflect interaction with carbonate. Boron isotopes highlight secondary processes such as adsorption/desorption onto clays in addition to mixings. At the Barcarès site (120m deep), the high salinity in some layers appear to be related neither to present day seawater intrusion, nor to Salses-Leucate lagoonwater intrusion. Groundwater chemical composition thus highlights binary mixing between fresh groundwater and inherited salty water together with cation exchange processes, water–rock interactions and, locally, sedimentary organic matter mineralisation probably enhanced by pyrite oxidation. Finally, combining the results of this study and those of Caballero and Ladouche (2015), we discuss the possible future evolution of this aquifer system under global change, as well as the potential management strategies needed to preserve quantitatively and qualitatively this water resource.

Abstract: The current global intrusion of seawater into coastal aquifers causes salinization of groundwater and thus significant degradation of its quality. This study quantified the effect of seawater intrusion and freshening events in coastal aquifers on trace elements (Li, B, Mn and Ba) across the fresh-saline water interface (FSI) and their possible use as indicators for these events. This was done by combining field data and column experiments simulating these events. The experiments enabled quantification of the processes affecting the trace element composition and examination of whether salinization and freshening events are geochemically reversible, which has been seldom investigated. The dominant process affecting trace element composition during salinization and freshening is ion exchange. The results of the experiments show that the concentrations of major cations and Li+ were reversible during salinization and freshening, whereas B, Mn2+ and Ba2+ were not. During salinization, Li+ and B were depleted due to sorption by 10 and 100μmol·L−1, respectively, to about half of their expected conservative concentrations. The relative depletion of Li+ increased with distance from the shore, representing the propagation of salinization. Ba2+ and Mn2+ were desorbed from the sediment during salinization and enriched by tenfold in the aqueous phase compared to their concentration in seawater ( 0.1 μeq·L−1). During freshening both were depleted by almost tenfold compared to their concentration in fresh groundwater ( 0.7 μeq·L−1). The depletion of Mn2+ is a sensitive marker for freshening because Mn2+ has a strong affinity to the solid phase. Moreover, this study shows that both Mn2+ and Ba2+ can be used as sensitive hydrogeochemical tools to distinguish between salinization and freshening events in the FSI zone in coastal aquifers.