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.

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.