Abstract: In this study a typical coastal karst aquifer, developed in lower Cretaceous limestones, on the western Mediterranean seashore (La Clape massif, southern France) was investigated. A combination of geochemical and isotopic approaches was used to investigate the origin of salinity in the aquifer. Water samples were collected between 2009 and 2011. Three groundwater groups (A, B and C) were identified based on the hydrogeological setting and on the Cl− concentrations. Average and maximum Cl− concentrations in the recharge waters were calculated (ClRef. and ClRef.Max) to be 0.51 and 2.85mmol/L, respectively). Group A includes spring waters with Cl− concentrations that are within the same order of magnitude as the ClRef concentration. Group B includes groundwater with Cl− concentrations that range between the ClRef and ClRef.Max concentrations. Group C includes brackish groundwater with Cl− concentrations that are significantly greater than the ClRef.Max concentration. Overall, the chemistry of the La Clape groundwater evolves from dominantly Ca–HCO3 to NaCl type. On binary diagrams of the major ions vs. Cl, most of the La Clape waters plot along mixing lines. The mixing end-members include spring waters and a saline component (current seawater or fossil saline water). Based on the Br/Clmolar ratio, the hypothesis of halite dissolution from Triassic evaporites is rejected to explain the origin of salinity in the brackish groundwater. Groundwaters display 87Sr/86Sr ratios intermediate between those of the limestone aquifer matrix and current Mediterranean seawater. On a Sr mixing diagram, most of the La Clape waters plot on a mixing line. The end-members include the La Clape spring waters and saline waters, which are similar to the deep geothermal waters that were identified at the nearby Balaruc site. The 36Cl/Cl ratios of a few groundwater samples from group C are in agreement with the mixing hypothesis of local recharge water with deep saline water at secular equilibrium within a carbonate matrix. Finally, PHREEQC modelling was run based on calcite dissolution in an open system prior to mixing with the Balaruc type saline waters. Modelled data are consistent with the observed data that were obtained from the group C groundwater. Based on several tracers (i.e. concentrations and isotopic compositions of Cl and Sr), calculated ratios of deep saline water in the mixture are coherent and range from 3% to 16% and 0% to 3% for groundwater of groups C and B, respectively. With regard to the La Clape karst aquifer, the extension of a lithospheric fault in the study area may favour the rise of deep saline water. Such rises occur at the nearby geothermal Balaruc site along another lithospheric fault. At the regional scale, several coastal karst aquifers are located along the Gulf of Lion and occur in Mezosoic limestones of similar ages. The 87Sr/86Sr ratios of these aquifers tend toward values of 0.708557, which suggests a general mixing process of shallow karst waters with deep saline fossil waters. The occurrence of these fossil saline waters may be related to the introduction of seawater during and after the Flandrian transgression, when the highly karstified massifs invaded by seawater, formed islands and peninsulas along the Mediterranean coast.

Abstract: Throughout the Mediterranean, salinization threatens water quality, especially in coastal areas. This salinization is the result of concomitant processes related to both seawater intrusion and water–rock interaction, which in some cases are virtually indistinguishable. In the Nurra region of northwestern Sardinia, recent salinization related to marine water intrusion has been caused by aquifer exploitation. However, the geology of this region records a long history from the Palaeozoic to the Quaternary, and is structurally complex and comprises a wide variety of lithologies, including Triassic evaporites. Determining the origin of the saline component of the Jurassic and Triassic aquifers in the Nurra region may provide a useful and more general model for salinization processes in the Mediterranean area, where the occurrence of evaporitic rocks in coastal aquifers is a common feature. In addition, due to intensive human activity and recent climatic change, the Nurra has become vulnerable to desertification and, in common with other Mediterranean islands, surface water resources periodically suffer from severe shortages. With this in mind, we report new data regarding brackish and surface waters (outcrop and lake samples) of the Na-Cl type from the Nurra region, including major ions and selected trace elements (B, Br, I, and Sr), in addition to isotopic data including δ18O, δD in water, and δ34S and δ18O in dissolved SO4. To identify the origin of the salinity more precisely, we also analysed the mineralogical and isotopic composition of Triassic evaporites. The brackish waters have Cl contents of up to 2025 mg L−1 , and the ratios between dissolved ions and Cl, with the exception of the Br / Cl ratio, are not those expected on the basis of simple mixing between rainwater and seawater. The δ18O and δD data indicate that most of the waters fall between the regional meteoric water line and the global meteoric water line, supporting the conclusion that they are meteoric in origin. A significant consequence of the meteoric origin of the Na-Cl-type water studied here is that the Br / Cl ratio, extensively used to assess the origin of salinity in fresh water, should be used with care in carbonate aquifers that are near the coast. Overall, δ34S and δ18O levels in dissolved SO4 suggest that water–rock interaction is responsible for the Na-Cl brackish composition of the water hosted by the Jurassic and Triassic aquifers of the Nurra, and this is consistent with the geology and lithological features of the study area. Evaporite dissolution may also explain the high Cl content, as halite was detected within the gypsum deposits. Finally, these Na-Cl brackish waters are undersaturated with respect to the more soluble salts, implying that in a climate evolving toward semi-arid conditions, the salinization process could intensify dramatically in the near future.