Hydrochemical assessment of freshening saline groundwater using multiple end-members mixing modeling: A study of Red River delta aquifer, Vietnam

In this study, we evaluated the water quality status (especially, salinity problems) and hydrogeochemical processes of an alluvial aquifer in a floodplain of the Red River delta, Vietnam, based on the hydrochemical and isotopic data of groundwater samples (n = 23) from the Kien Xuong district of the Thai Binh province. Following the historical inundation by paleo-seawater during coastal progradation, the aquifer has been undergone progressive freshening and land reclamation to enable settlements and farming. The hydrochemical data of water samples showed a broad hydrochemical change, from Na-Cl through Na-HCO₃ to Ca-HCO₃ types, suggesting that groundwater was overall evolved through the freshening process accompanying cation exchange. The principal component analysis (PCA) of the hydrochemical data indicates the occurrence of three major hydrogeochemical processes occurring in an aquifer, namely: 1) progressive freshening of remaining paleo-seawater, 2) water-rock interaction (i.e., dissolution of silicates), and 3) redox process including sulfate reduction, as indicated by heavy sulfur and oxygen isotope compositions of sulfate. To quantitatively assess the hydrogeochemical processes, the end-member mixing analysis (EMMA) and the forward mixing modeling using PHREEQC code were conducted. The EMMA results show that the hydrochemical model with the two-dimensional mixing space composed of PC 1 and PC 2 best explains the mixing in the study area; therefore, we consider that the groundwater chemistry mainly evolved by mixing among three end-members (i.e., paleo-seawater, infiltrating rain, and the K-rich groundwater). The distinct depletion of sulfate in groundwater, likely due to bacterial sulfate reduction, can also be explained by EMMA. The evaluation of mass balances using geochemical modeling supports the explanation that the freshening process accompanying direct cation exchange occurs through mixing among three end-members involving the K-rich groundwater. This study shows that the multiple end-members mixing model is useful to more successfully assess complex hydrogeochemical processes occurring in a salinized aquifer under freshening, as compared to the conventional interpretation using the theoretical mixing line based on only two end-members (i.e., seawater and rainwater).