Geochemical and isotopic evidence for palaeo-seawater intrusion into the south coast aquifer of Laizhou Bay, China

This research aims to improve the current knowledge of groundwater salinisation processes in coastal aquifers using combined hydrochemical and isotopic parameters and inverse hydrochemical modelling. Field investigations were conducted in Laizhou Bay, which is the area most seriously affected by seawater intrusion in north China. During three sampling campaigns along a vertical transect in the Changyi-Liutuan area, 95 ground- and surface-water samples were collected for major ion and isotope analysis (²H/¹⁸O, ³H, ¹⁴C, ³⁴S). The groundwater changes along the general flowpath towards the coast from fresh (<1 g/L), brackish (1-10 g/L), saline (10-100 g/L) to brine water (>100 g/L). Molar Cl/Br ratios are close to those of seawater in almost all groundwater samples, indicating that brines and deep seawater evolved from different events of palaeo-seawater intrusion. Depleted isotopic signatures of brines and deep saline water point to a former, initially depleted seawater reservoir due to runoff dilution. Tritium and ¹⁴C activities in deep saline water below confining units indicate isolation from modern precipitation and significant residence times. Brine water shows a wide range of ³H and ¹⁴C ages due to the complex conditions of mixing without isolation from modern groundwater. Sulphur-34 isotope ratios support seawater intrusion as a possible salt origin, although this parameter does not exclude gypsum dissolution. The combined use of Cl and ¹⁸O yields four different end-members of groundwater, and three different mixing scenarios were identified explaining the hydrochemical composition of groundwater samples with intermediate salinity in the different areas. To improve understanding of the various water types and their related processes in a spatial context, a conceptual model was developed integrating the results derived from the presented data in a vertical cross-section. Results of three inverse modelling simulations using PHREEQC-2 show that all hypothetical mixing scenarios derived from conservative components are thermodynamically feasible. In all scenarios, mixing, ion exchange, dissolution of dolomite and precipitation of gypsum and calcite account for the hydrochemical changes.