Abstract: Summary A hydrochemical-isotopic investigation of the Laizhou Bay Quaternary aquifer in north China provides new insights into the hydrodynamic and geochemical relationships between freshwater, seawater and brine at different depths in coastal sediments. Saltwater intrusion mainly occurs due to two cones of depression caused by concentrated exploitation of fresh groundwater in the south, and brine water for salt production in the north. Groundwater is characterized by hydrochemical zonation of water types (ranging from Ca–HCO3 to Na–Cl) from south to north, controlled by migration and mixing of saline water bodies with the regional groundwater. The strong adherence of the majority of ion/Cl ratios to mixing lines between freshwater and saline water end-members (brine or seawater) indicates the importance of mixing under natural and/or anthropogenic influences. Examination of the groundwater stable isotope δ18O and δ2H values (between −9.5‰ and −3.0‰ and −75‰ and −40‰, respectively) and chloride contents (∼2 to 1000meq/L) of the groundwater indicate that the saline end-member is brine rather than seawater, and most groundwater samples plot on mixing trajectories between fresh groundwater (δ18O of between −6.0‰ and −9.0‰; Cl<5meq/L) and sampled brines (δ18O of approximately −3.0‰ and Cl>1000meq/L). Locally elevated Na/Cl ratios likely result from ion exchange in areas of long-term freshening. The brines, with radiocarbon activities of ∼30 to 60 pMC likely formed during the Holocene as a result of the sequence of transgression-regression and evaporation; while deep, fresh groundwater with depleted stable isotopic values (δ18O=−9.7‰ and δ2H=−71‰) and low radiocarbon activity (<20 pMC) was probably recharged during a cooler period in the late Pleistocene, as is common throughout northern China. An increase in the salinity and tritium concentration in some shallow groundwater sampled in the 1990s and re-sampled here indicates that intensive brine extraction has locally resulted in rapid mixing of young, fresh groundwater and saline brine. The δ18O and δ2H values of brines (∼−3.0‰ and −35‰) are much lower than that of modern seawater, which could be explained by 1) mixing of original (δ18O enriched) brine that was more saline than presently observed, with fresh groundwater recharged by precipitation and/or 2) dilution of the palaeo-seawater with continental runoff prior to and/or during brine formation. The first mechanism is supported by relatively high Br/Cl molar ratios (1.7×10−3–2.5×10−3) in brine water compared with ∼1.5×10−3 in seawater, which could indicate that the brines originally reached halite saturation and were subsequently diluted with fresher groundwater over the long-term. Decreasing 14C activities with increasing sampling depth and increasing proximity to the coastline indicate that the south coastal aquifer in Laizhou Bay is dominated by regional lateral flow, on millennial timescales.

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.