Abstract: The current global intrusion of seawater into coastal aquifers causes salinization of groundwater and thus significant degradation of its quality. This study quantified the effect of seawater intrusion and freshening events in coastal aquifers on trace elements (Li, B, Mn and Ba) across the fresh-saline water interface (FSI) and their possible use as indicators for these events. This was done by combining field data and column experiments simulating these events. The experiments enabled quantification of the processes affecting the trace element composition and examination of whether salinization and freshening events are geochemically reversible, which has been seldom investigated. The dominant process affecting trace element composition during salinization and freshening is ion exchange. The results of the experiments show that the concentrations of major cations and Li+ were reversible during salinization and freshening, whereas B, Mn2+ and Ba2+ were not. During salinization, Li+ and B were depleted due to sorption by 10 and 100μmol·L−1, respectively, to about half of their expected conservative concentrations. The relative depletion of Li+ increased with distance from the shore, representing the propagation of salinization. Ba2+ and Mn2+ were desorbed from the sediment during salinization and enriched by tenfold in the aqueous phase compared to their concentration in seawater ( 0.1 μeq·L−1). During freshening both were depleted by almost tenfold compared to their concentration in fresh groundwater ( 0.7 μeq·L−1). The depletion of Mn2+ is a sensitive marker for freshening because Mn2+ has a strong affinity to the solid phase. Moreover, this study shows that both Mn2+ and Ba2+ can be used as sensitive hydrogeochemical tools to distinguish between salinization and freshening events in the FSI zone in coastal aquifers.

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.