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: Seawater intrusion (SWI) has led to salinization of fresh groundwater reserves in coastal areas worldwide and has forced the closure of water supply wells. There is a paucity of well-documented studies that report on the reversal of SWI after the closure of a well field. This study presents data from the coastal carbonate aquifer in northeast China, where large-scale extraction has ceased since 2001 after salinization of the main well field. The physical flow and concomitant hydrogeochemical processes were investigated by analyzing water level and geochemical data, including major ion chemistry and stable water isotope data. Seasonal water table and salinity fluctuations, as well as changes of δ2H–δ18O values of groundwater between the wet and dry season, suggest local meteoric recharge with a pronounced seasonal regime. Historical monitoring testifies of the reversibility of SWI in the carbonate aquifer, as evidenced by a decrease of the Cl− concentrations in groundwater following restrictions on groundwater abstraction. This is attributed to the rapid flushing in this system where flow occurs preferentially along karst conduits, fractures and fault zones. The partially positive correlation between δ18O values and TDS concentrations of groundwater, as well as high NO3− concentrations (\textgreater39mg/L), suggest that irrigation return flow is a significant recharge component. Therefore, the present-day elevated salinities are more likely due to agricultural activities rather than SWI. Nevertheless, seawater mixing with fresh groundwater cannot be ruled out in particular where formerly intruded seawater may still reside in immobile zones of the carbonate aquifer. The massive expansion of fish farming in seawater ponds in the coastal zone poses a new risk of salinization. Cation exchange, carbonate dissolution, and fertilizer application are the dominant processes further modifying the groundwater composition, which is investigated quantitatively using hydrogeochemical models.