Abstract: Understanding the interference of natural processes and anthropogenic activities in geochemical evolution of groundwater is vital for groundwater sustainable management in water-stressed regions. This study is devoted to the identification of the main factors controlling the evolution of groundwater chemistry by the combined use of hydrogeochemical indicators along with isotope tracers in the Heilongdong Spring Basin, North China. Thirty-nine groundwater samples and twelve surface water samples were collected, and major ions and stable isotopes were measured during the two campaigns (December 2017 and August 2018). The isotope approach indicates that the groundwater is recharged by precipitation infiltration after evaporation, and interacts with surface water along preferential flow paths in fault zones and karst conduits. Currently, the main chemical facies of groundwater evolve from Ca-HCO3 and Ca-Mg-HCO3 types with low TDS, through Ca-Mg-HCO3-SO4 and Ca-HCO3-SO4 types with moderate TDS, to Ca-SO4, Ca-SO4-Cl and CaCl types with high TDS. Apart from natural processes (involving dissolution/precipitation of minerals, cation exchange, and evaporation) regulating the groundwater quality, the stagnant zones also play a crucial role in the formation of severe localized nitrate contamination. The deterioration in groundwater quality can be attributed to anthropogenic factors (including the change in groundwater exploitation, the leaching of solid waste, and the overuse of agricultural fertilizers). The high loads of agricultural fertilizers in irrigation return flows are likely to be the main contributor of the dissolved nitrate in groundwater. The findings of this work not only have important implications for groundwater sustainable utilization, but also could serve as a template for other rapidly industrialized and water-stressed regions.

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.