Abstract: In the southern coastal plain of Laizhou Bay, due to intensive exploitation of groundwater since the early 1970s, the shallow aquifer has been severely influenced by saltwater intrusion, which causes the extraction to shift from shallow to deeper aquifer changing the hydrogeological condition greatly. This study was conducted to investigate the groundwater salinization using hydrochemistry and H, O and Li isotope data. Dissolved Li shows a linear correlation with Cl and Br in seawater, brine and saline groundwater indicating the marine Li source, whereas the enrichment of Li in surface water, brackish and fresh groundwater is impacted by dissolution of silicate minerals. The analyses of hydrochemistry and isotopes (H, O and Li) indicate that brine originated from seawater evaporation, followed by mixing processes and some water-rock interactions; shallow saline groundwater originated from brine diluted with seawater and fresh groundwater; deep saline groundwater originated from seawater intrusion. The negative correlation of δ(7)Li and Li/Na in surface water, brackish and fresh groundwater is contrary to the general conclusion, indicating the slow weathering of silicate minerals and hydraulic interaction between surface water and shallow groundwater in this area. The analyses of hydrochemistry and isotopes (Li, H and O) can well identify the salinity sources and isotope fractionation in groundwater flow and mixing, especially groundwater with high TDS. As both mixing with saltwater and isotope fractionation can explain the combination of high δ(7)Li and low TDS in brackish groundwater, isotope fractionation may limit their use in recognizing salinity sources of groundwater with low TDS.

Abstract: Economically developed coastal areas have a high water demand, and their groundwater resources can be threatened by salinization. Many methods and tracers have been used to discriminate the source of salinization because a single method does not yield reliable results. In this paper, the shallow confined coastal plain aquifer, north of the downstream Yangtze River in China, is used as a case study to investigate the origin of the salinity and the relevant geochemical processes for this aquifer. Multiple environmental tracers of major ions, minor ions (Br−, I−), and isotopes (18O, 2H, 13C, 87Sr, 3H, 14C) were used so as to provide reliable conclusions. The TDS distribution of the aquifer has an increasing trend, from below 500 mg/L in the inland areas to more than 20,000 mg/L around the southeast coastline. The water chemical type evolves from HCO3-Ca to Cl-Na as the TDS increases. The results suggest that the groundwater salinity is influenced by seawater intrusion. The seawater proportions in the groundwater samples range from 0.07% to 94.41% and show the same spatial distribution pattern as TDS. The 3H and 14C values show that the highest salinity was mainly caused by a seawater transgression around 6000a B.P. The aquifer is also affected by other hydrogeochemical processes: base exchange has enriched Ca2+ and depleted K+ and Na+, sulfate reduction has reduced the concentration of SO42− and enriched HCO3−, and iodine-rich organic matter decomposition has enriched the concentration of I−. The iodine enrichment also suggests paleo-seawater intrusion. In addition, the precipitation of carbonate minerals has decreased the concentration of Ca2+, Mg2+, and HCO3−, albeit to a limited extent.