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: In the coastal region of Bangladesh, groundwater is mainly used for domestic and agricultural purposes, but salinization of many groundwater resources limits its suitability for human consumption and practical application. This paper reports the results of a study that has mapped the salinity distribution in different aquifer layers up to a depth of 300 m in a region bordering the Bay of Bengal based on the main hydrochemistry and has investigated the origin of the salinity using Cl/Br ratios of the samples. The subsurface consists of a sequence of deltaic sediments with an alternation of more sandy and clayey sections in which several aquifer layers can be recognized. The main hydrochemistry shows different main water types in the different aquifers, indicating varying stages of freshening or salinization processes. The most freshwater, soft NaHCO3-type water with Cl concentrations mostly below 100 mg/l, is found in the deepest aquifer at 200-300 m below ground level (b.g.l.), in which the fresh/saltwater interface is pushed far to the south. Salinity is a main problem in the shallow aquifer systems, where Cl concentrations rise to nearly 8000 mg/l and the groundwater is mostly brackish NaCl water. Investigation of the Cl/Br ratios has shown that the source of the salinity in the deep aquifer is mixing with old connate seawater and that the saline waters in the more shallow aquifers do not originate from old connate water or direct seawater intrusion, but are derived from the dissolution of evaporite salts. These must have been formed in a tidal flat under influence of a strong seasonal precipitation pattern. Long dry seasons with high evaporation rates have evaporated seawater from inundated gullies and depressions, leading to salt precipitation, while subsequent heavy monsoon rains have dissolved the formed salts, and the solution has infiltrated in the subsoil, recharging groundwater.

Abstract: Submarine groundwater discharge (SGD) is an important source of nutrients and metals to the coastal ocean, affects coastal ecosystems, and is gaining recognition as a relevant water resource. SGD is usually quantified using geochemical tracers such as radon or radium. However, a few studies have also used dissolved silicon (DSi) as a tracer for SGD, as DSi is usually enriched in groundwater when compared to surface waters. In this study, we discuss the potential of DSi as a tracer in SGD studies based on a literature review and two case studies from contrasting environments. In the first case study, DSi is used to calculate SGD fluxes in a tropical volcanic-carbonate karstic region (southern Java, Indonesia), where SGD is dominated by terrestrial groundwater discharge. The second case study discusses DSi as a tracer for marine SGD (i.e., recirculated seawater) in the tidal flat area of Spiekeroog (southern North Sea), where SGD is dominantly driven by tidal pumping through beach sands. Our results indicate that DSi is a useful tracer for SGD in various lithologies (e.g., karstic, volcanic, complex) to quantify terrestrial and marine SGD fluxes. DSi can also be used to trace groundwater transport processes in the sediment and the coastal aquifer. Care has to be taken that all sources and sinks of DSi are known and can be quantified or neglected. One major limitation is that DSi is used by siliceous phytoplankton and therefore limits its applicability to times of the year when primary production of siliceous phytoplankton is low. In general, DSi is a powerful tracer for SGD in many environments. We recommend that DSi should be used to complement other conventionally used tracers, such as radon or radium, to help account for their own shortcomings.