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 hydrogeological unit of Aguadulce (Campo de Dalías aquifers, SE Spain) has a complex geometry. This fact, together with a continuous rise in water demand due to intensive agriculture and tourism create problems for groundwater quantity and quality. In this paper classic geochemical tools managed by means of GIS software and geochemical simulations are combined to delineate, identify and locate the possible physicochemical processes acting in the Aguadulce groundwater. Two main aquifers can be distinguished: the carbonate or lower aquifer of Triassic age, and the calcodetritic or upper aquifer of Plio-Quaternary age. Groundwaters from the latter are more saline and, assuming all chlorinity originates from seawater intrusion, the seawater contribution to their composition would be up to 7%. Nevertheless the carbonate aquifer appears not to be homogeneous: it is compartmentalised into 4 zones where different processes explain the different groundwaters compositions. Zone 4 samples (E margin of the carbonate aquifer) resemble those of the Plio-Quaternary aquifer, where calcite precipitation, dolomite and gypsum dissolution and some cation exchange (water–rock interaction) together with seawater–freshwater mixing occur. In contrast, water–rock interaction predominates in zones 1 and 3 of the carbonate aquifer. Moreover, zone 2 samples, located between zones 1 and 3, are explained by water–rock interaction in addition to mixing with Plio-Quaternary aquifer waters. The combination of geochemical simulations with GIS and hydrogeochemical analyses has proven to be effective in identifying and locating the different physicochemical processes in the aquifer areas, thus improving understanding of hydrogeochemistry in complex aquifers.