Hydrochemical evolution processes of multiple-water quality interfaces (fresh/saline water, saline water/brine) on muddy coast under pumping conditions.

A thorough understanding of the evolution of coastal brine-bearing groundwater systems under the influence of human activities contributes to the sustainable use of coastal groundwater resources. Therefore, this study comprehensively investigated the processes associated with hydrochemical changes in groundwater during brine exploitation based on long-term monitoring data. The dataset comprised 102 samples (including groundwater, seawater, rain and river samples) collected from 1966 to 2021 to capture the hydrochemical variability. Significant changes in the brine water table and concentration between the pre-overexploitation period (1965-2000) and the exploitation period (2000-2021) are observed. From the relationship between stable isotope (δ18O and δ2H) values and Cl- contents, shallow saline water (SSW) near the drawdown cone (with δ18O and δ2H values of -4.66 ‰ ~ -3.57 ‰ and - 42.1 ‰ ~ -32.8 ‰, respectively) is similar geochemically to the brine inside the drawdown cone (with values of -4.30 ‰ ~ -3.10 ‰ and - 39.0 ‰ ~ -32.3 ‰, respectively), indicating that the SSW has a recharge effect on the underground brine. The delta values of major cations were calculated to analyze the hydrochemical processes at different water quality interfaces (saline/freshwater interface, salinewater/brine interface). The results demonstrated that the SSW and deep saline water (DSW) at the offshore brine/saline water interface undergo seawater intrusion, where SSW undergoes a salinization process with cation exchange (Na+ is exchanged for Ca2+ and Mg2+ in clay), while DSW undergoes a freshening process. The SSW at the saline/freshwater interface is affected by freshwater pumping, and the DSW undergoes a salinization process influenced by brine intrusion presenting the common salinization process with cation exchange. The hydrochemical model shows that the brine concentration recovered during the restricted exploitation stage due to the dissolution of gypsum and halite. If no measures are taken to restrict exploitation, then brine will eventually be replaced by saline water.