Isotopic and geochemical evolution of ground and surface waters in a karst dominated geological setting: a case study from Belize,Central America

Analysis of stable isotopes and major ions in groundwater and surface waters in Belize, Central America was carried out to identify processes that may affect drinking water quality. Belize has a subtropical rainforest/savannah climate with a varied landscape composed predominantly of carbonate rocks and clastic sediments. Stable oxygen (δ¹⁸O) and hydrogen (δD) isotope ratios for surface and groundwater have a similar range and show high d-excess (10–40.8‰). The high d-excess in water samples suggest secondary continental vapor flux mixing with incoming vapor from the Caribbean Sea. Model calculations indicate that moisture derived from continental evaporation contributes 13% to overhead vapor load. In surface and groundwater, concentrations of dissolved inorganic carbon (DIC) ranged from 5.4 to 112.9 mg C/l and δ¹³C_DIC ranged from −7.4 to −17.4‰. SO₄², Ca²⁺ and Mg²⁺ in the water samples ranged from 2–163, 2–6593 and 2–90 mg/l, respectively. The DIC and δ¹³C_DIC indicate both open and closed system carbonate evolution. Combined δ¹³C_DIC and Ca²⁺, Mg²⁺, and SO₄²⁻ suggest additional groundwater evolution by gypsum dissolution and calcite precipitation. The high SO₄²⁻content of some water samples indicates regional geologic control on water quality. Similarity in the range of δ¹⁸O, δD and δ¹³C_DIC for surface waters and groundwater used for drinking water supply is probably due to high hydraulic conductivities of the karstic aquifers. The results of this study indicate rapid recharge of groundwater aquifers, groundwater influence on surface water chemistry and the potential of surface water to impact groundwater quality and vise versa.     

Isotope Geochemistry of Groundwater from Fractured Dolomite Aquifers in Central Slovenia

The hydrogeochemistry and isotope geochemistry of groundwater from 85 wells in fractured dolomite aquifers of Central Slovenia were investigated. This groundwater represents waters strongly influenced by chemical weathering of dolomite with an average of δ¹³C_CARB value of +2.2 ‰. The major groundwater geochemical composition is HCO₃ ^? > Ca²⁺ > Mg²⁺. Several differences in hydrogeochemical properties among the classes of dolomites were observed when they were divided based on their age and sedimentological properties, with a clear distinction of pure dolomites exhibiting high Mg²⁺/Ca²⁺ ratios and low Na⁺, K⁺ and Si values. Trace element and nutrient concentrations (SO₄ ^2?, NO₃ ^?) were low, implying that karstic and fractured dolomite aquifers are of good quality to be used as tap water. Groundwater was generally slightly oversaturated with respect to calcite and dolomite, and dissolved CO₂ was up to 46 times supersaturated relative to the atmosphere. The isotopic composition of oxygen (δ¹⁸O_H2O), hydrogen (δD_H2O) and tritium ranged from ?10.3 to ?8.4 ‰, from ?68.5 to ?52.7 ‰ and from 3.5 TU to 10.5 TU, respectively. δ¹⁸O and δD values fell between the GMWL (Global Meteoric Water Line) and the MMWL (Mediterranean Meteoric Water Line) and indicate recharge from precipitation with little evaporation. The tritium activity in groundwater suggests that groundwater is generally younger than 50 years. δ¹³C_DIC values ranged from ?14.6 to ?9.3 ‰ and indicated groundwater with a contribution of degraded organic matter/dissolved inorganic carbon in the aquifer. The mass balances for groundwater interacting with carbonate rocks suggested that carbonate dissolution contributes from 43.7 to 65.4 % and degradation of organic matter from 34.6 to 56.3 %.     

Hydrogeochemical and isotopic evidences of the groundwater regime in Datong Basin, Northern China

Datong Basin is one of the Cenozoic faulted basins in Northern China’s Shanxi province, where groundwater is the major source of water supply. The results of hydrochemical investigation show that along the groundwater flow path, from the margins to the lower-lying central parts of the basin, groundwater generally shows increases in concentrations of TDS, HCO₃ ^?, SO₄ ^2?, Cl^?, Na⁺ and Mg²⁺ (except for Ca²⁺ content). Along the basin margin, groundwater is dominantly of Ca–HCO₃ type; however, in the central parts of the basin it becomes more saline with Na–HCO₃-dominant or mixed-ion type. The medium-deep groundwater has chemical compositions similar to those of shallow groundwater, except for the local area affected by human activity. From the mountain front to the basin area, shallow groundwater concentrations of major ions increase and are commonly higher than those in medium-deep aquifers, due to intense evapotranspiration and anthropogenic contamination. Hydrolysis of aluminosilicate and silicate minerals, cation exchange and evaporation are prevailing geochemical processes occurring in the aquifers at Datong Basin. The isotopic compositions indicate that meteoric water is the main source of groundwater recharge. Evaporation is the major way of discharge of shallow groundwater. The groundwater in medium-deep aquifers may be related to regional recharges of rainwater by infiltrating along the mountain front faults, and of groundwater permeating laterally from bedrocks of the mountain range. However, in areas of groundwater depression cones, groundwater in the deep confined aquifers may be recharged by groundwater from the upper unconfined aquifer through aquitards.     

Residence time of Chalk groundwaters in the Paris Basin and the North German Basin: a geochemical approach

The comparative geochemical and isotopic study of confined and unconfined Chalk groundwaters of the Paris Basin and the N German Basin proves a significant chemical evolution during groundwater flow from the recharge zones to the deep confined aquifer. Different time dependent geochemical parameters have been tested as dating tools: Cation ratios (Sr²⁺/Ca²⁺, Mg²⁺/Ca²⁺), N–NO⁻₃, noble gas contents as paleotemperature indicators (Ne, Ar, Kr, Xe), radiogenic He, ¹³C, ¹⁴C, ¹⁸O, ²H, ³H. Cation ratios and ¹³C show the importance of incongruent dissolution processes in the Chalk aquifer. Water–rock interactions were taken into account in a multi-step dissolution model to determine radiocarbon groundwater ages. The oldest waters in the confined part of the Paris basin Chalk with maximum ¹⁴C ages of 14,000 a B.P. contain pleistocene recharge components as can be shown by a stable isotope depletion and noble gas temperatures significantly lower than in recent groundwaters. Chalk waters at the Lägerdorf site in Northern Germany show a distinct stratification with respect to residence times and hydrochemistry.     

Hydrogeological and hydrochemical investigation of groundwater using environmental isotopes (18O, 2H, 3H, 14C) and chemical tracers: a case study of the intermediate aquifer,Sfax, southeastern Tunisia

Major element concentrations and stable (δ¹⁸O and δ²H) and radiogenic (³H and ¹⁴C) isotopes in groundwater have proved useful tracers for understanding the geochemical processes that control groundwater mineralization and for identifying recharge sources in the semi-arid region of Sfax (southeastern Tunisia). Major-ion chemical data indicate that the origins of the salinity in the groundwater are the water–rock interactions, mainly the dissolution of evaporitic minerals, as well as the cation exchange with clay minerals. The δ¹⁸O and δ²H relationships suggest variations in groundwater recharge mechanisms. Strong evaporation during recharge with limited rapid water infiltration is evident in the groundwater of the intermediate aquifer. The mixing with old groundwater in some areas explains the low stable isotope values of some groundwater samples. Groundwaters from the intermediate aquifer are classified into two main water types: Ca-Na-SO₄ and Ca-Na-Cl-SO₄. The high nitrate concentrations suggest an anthropogenic source of nitrogen contamination caused by intensive agricultural activities in the area. The stable isotopic signatures reveal three water groups: non-evaporated waters that indicate recharge by recent infiltrated water; evaporated waters that are characterized by relatively enriched δ¹⁸O and δ²H contents; and mixed groundwater (old/recent) or ancient groundwater, characterized by their depleted isotopic composition. Tritium data support the existence of recent limited recharge; however, other low tritium values are indicative of pre-nuclear recharge and/or mixing between pre-nuclear and contemporaneous recharge. The carbon-14 activities indicate that the groundwaters were mostly recharged under different climatic conditions during the cooler periods of the late Pleistocene and Holocene.

     

Hydrogeochemical investigation of surface and groundwater composition in an irrigated land in Central Tunisia

Major element concentrations, stable (δ¹⁸O and δ²H) and radiogenic (³H, ¹⁴C) isotopes determined in groundwater provided useful initial tracers for understanding the processes that control groundwater mineralization and identifying recharge sources in semi-arid Cherichira basin (central Tunisia).Chemical data based on the chemistry of several major ions has revealed that the main sources of salinity in the groundwaters are related to the water–rock interaction such as the dissolution of evaporitic and carbonate minerals and some reactions with silicate and feldspar minerals.The stable isotope compositions provide evidence that groundwaters are derived from recent recharge. The δ¹⁸O and δ²H relationships implied rapid infiltration during recharge to both the Oligocene and Quaternary aquifers, with only limited evaporation occurring in the Quaternary aquifer.Chemical and isotopic signatures of the reservoir waters show large seasonal evolution and differ clearly from those of groundwaters.Tritium data support the existence of recent recharge in Quaternary groundwaters. But, the low tritium values in Oligocene groundwaters are justified by the existence of clay lenses which limit the infiltration of meteoric water in the unsaturated zone and prolong the groundwater residence time.Carbon-14 activities confirm that groundwaters are recharged from the surface runoff coming from precipitation.     

Hydrogeochemical Analysis of Processes Through Modeling of Seawater Intrusion Impacts in Biscayne Aquifer Water Quality,USA

Hydrogeochemical processes that accompany seawater intrusion in coastal aquifers can alter the resulting water quality and are important ingredients in coastal aquifer management. The presence of dissolution–precipitation reactions and ion exchange in the mixing zone of the Biscayne aquifer (FL, USA) are suggested based on changes in major ion concentrations and mineral saturation indices (SI). Major ion concentrations from 11 groundwater samples are compared with theoretical mixing between freshwater and seawater. PHREEQC code was used to calculate saturation indices of the samples with respect to common phases in the Biscayne aquifer. High Ca²⁺ and HCO₃ ^? content of the samples is typical of waters in contact with carbonate aquifers. Water quality of the samples is mainly attributed to mixing and precipitation–dissolution reactions with calcite and dolomite. The samples were saturated with calcite (SI ~ 0) and undersaturated for dolomite (SI < 0), while a few samples showed dolomite saturation. Because gypsum and halite SI could be predicted by theoretical mixing, reactions with those minerals, if present, are thought to be insignificant. In the active intrusion areas, cation exchange also appears to modify water quality leading to excess Ca²⁺, but depleted Na⁺, Mg²⁺ and K⁺ concentrations. On the other hand, samples from previous intrusion areas plotted very close to the theoretical mixing line and approached equilibrium with the seawater.     

Investigation of the hydrogeochemical processes in an alluvial channel aquifer located in a typical Karoo Basin of Southern Africa

An investigation was conducted to assess the hydrogeochemical processes of an alluvial channel aquifer located in a typical Karoo Basin of Southern Africa. The investigation was aimed at identifying and describing the groundwater chemistry evolution and its contribution to the overall groundwater quality. X-ray fluorescent spectrometry (XRF) and X-ray diffractometry (XRD) analyses were performed on geological samples to identify and quantify the major element oxides and minerals. The study utilises the conventional Piper diagram, bivariate plots and PHREEQC hydrogeochemical model to analyse groundwater chemistry data obtained during the wet (February and May) and dry seasons (August and December) of 2011. The XRF and XRD results show that the channel deposits are dominated by SiO₂ element oxides and quartz minerals, thus elevated concentrations of silicon (Si⁴⁺) were found in the groundwater. Dolomite and calcite minerals were also detected in the unconsolidated aquifer sediments. The detailed study of the alluvial aquifer system has shown that dissolution of dolomite and calcite minerals and ion exchange are the dominant hydrogeochemical processes influencing the groundwater quality. The groundwater evolves from Ca²⁺–Mg²⁺–HCO₃ ^? recharge water that goes through ion exchange with Na⁺ in the clay-silt sediment to give a Na⁺–HCO₃ ^? water type. The groundwater is supersaturated with respect to quartz, dolomite and calcite minerals. The study shows the potential usefulness of simple bivariate plots as a complimentary tool to the conventional methods for analyzing groundwater hydrogeochemical processes.     

Groundwater recharge and evolution in the Dunhuang Basin,northwestern China

Groundwater recharge and evolution in the Quaternary aquifer beneath the Dunhuang Basin was investigated using chemical indicators, stable isotopes, and radiocarbon data to provide guidance for regional water management. The quality of groundwater and surface water is generally good with low salinity and it is unpolluted. The dissolution of halite and sylvite from fine-grained sediments controls concentrations of Na⁺ and K⁺ in the groundwater, but Na⁺/Cl⁻ molar ratios >1 in all samples are also indicative of weathering of feldspar contributing to excess Na⁺. The dissolution of carbonate minerals yields Ca²⁺ to the groundwater, thereby exerting a strong influence on groundwater salinity. The δ¹⁸O and δ²H values in unconfined groundwater are enriched along the groundwater flow path from SW to NE. In contrast, confined groundwater was depleted in heavy isotopes, with mean values of −10.4‰ δ¹⁸O and −74.4‰ δ²H. Compared with the precipitation values, all of the groundwater samples were strongly depleted in heavy isotopes, indicating that modern direct recharge to the groundwater aquifers in the plains area is quite limited. The unconfined water is generally young with radiocarbon values of 64.9–79.6 pmc. In the northern basin, radiocarbon content in the confined groundwater is less than 15 pmc and an uncorrected age of ∼15 ka, indicates that this groundwater was recharged during a humid climatic phases of the late Pleistocence or early Holocene. The results have important implications for inter-basin water allocation programmes and groundwater management in the Dunhuang Basin.     

Hydrogeochemical evaluation of fractured Limestone aquifer by applying a geochemical model in eastern Nile Valley,Egypt

Rock water interactions play an important role in the flow of groundwater. Groundwater samples were collected from deep production wells with depths ranging from 120 to 230 m. Complete chemical analysis of 40 groundwater samples was collected from the fractured limestone aquifer including major cations (Na⁺, K⁺, Ca²⁺, Mg²⁺) and major anions (Cl^?, SO₄ ^2?, HCO₃ ^?, CO₃ ^2?). A geochemical modeling (NETPATH Software) was applied for environmental simulate net geochemical mass-balance reactions between initial and final waters along a hydrologic flow path. This program simulates selected evolutionary waters for every possible combination of the plausible phases that account for the composition of a selected set of chemical constraints in the system. The groundwater of the Eocene aquifer mainly belongs to fairly fresh water with salinity contents ranging from 228 to 3595 ppm. The measured groundwater levels range between 8 and 25 m near the river Nile to the limestone plateau (eastwards). Consequently, groundwater flows from east to westward toward the river Nile. Groundwater aquifer in the study area is mainly composed of fractured limestone; the saturated states of the PCO₂, calcite, aragonite, dolomite, siderite, gypsum, anhydrite, hematite, and goethite in addition to H₂ gas were estimated. The undersaturated state of carbon dioxide reflects closed conditions and very low probability of recent recharge, and it reveals also the high tendency of water to precipitates carbonate species. Undersaturation by carbonate minerals is only restricted to some pockets distributed on the different places of the aquifer in the study area. The majority of groundwater samples of Eocene aquifer in the study area indicated that groundwater is not suitable for irrigation with treatment and requires good drainage.     

Distinct groundwater recharge sources and geochemical evolution of two adjacent sub-basins in the lower Shule River Basin,northwest China

Based on analysis of groundwater hydrogeochemical and isotopic data, this study aims to identify the recharge sources and understand geochemical evolution of groundwater along the downstream section of the Shule River, northwest China, including two sub-basins. Groundwater samples from the Tashi sub-basin show markedly depleted stable isotopes compared to those in the Guazhou sub-basin. This difference suggests that groundwater in the Tashi sub-basin mainly originates from meltwater in the Qilian Mountains, while the groundwater in the Guazhou sub-basin may be recharged by seepage of the Shule River water. During the groundwater flow process in the Tashi sub-basin, minerals within the aquifer material (e.g., halite, calcite, dolomite, gypsum) dissolve in groundwater. Mineral dissolution leads to strongly linear relationships between Na⁺ and Cl^? and between Mg²⁺+ Ca²⁺ and SO₄ ^2??+?HCO₃ ^?, with stoichiometry ratios of approximately 1:1 in both cases. The ion-exchange reaction plays a dominant role in hydrogeochemical evolution of groundwater in the Guazhou sub-basin and causes a good linear relationship between (Mg²⁺+ Ca²⁺)–(SO₄ ^2??+?HCO₃ ^?) and (Na⁺+ K⁺)–Cl^? with a slope of ?0.89 and also results in positive chloroalkaline indices CAI 1 and CAI 2. The scientific results have implications for groundwater management in the downstream section of Shule River. As an important irrigation district in Hexi Corridor, groundwater in the Guazhou sub-basin should be used sustainably and rationally because its recharge source is not as abundant as expected. It is recommended that the surface water should be used efficiently and routinely, while groundwater exploitation should be limited as much as possible.     

Changes in groundwater chemistry due to metallurgical activities in an alluvial aquifer in the Moa area (Cuba)

The aim of this work is to evaluate the changes in groundwater chemistry in an alluvial aquifer in the Moa area. Surface and ground water, metallurgical waste and various geological material samples were collected in order to evaluate groundwater composition. The results show that the alluvial aquifer is polluted with SO₄^2-, Mg²⁺and heavy metals. According to its major components in the alluvial aquifer, two types of groundwater are identified: magnesi-bicarbonated and sulphate-magnesic. Maximum SO₄^2– and Mg²⁺ contents are more than 1000 mg/L, and are four times higher than the acceptable levels for human consumption of water. The high values of Cr(VI), Ni(II), Mn(II) Fe_(total), SO₄^2– and Mg²⁺ in alluvial aquifers are due to polluted recharge from metallurgical waste from the tailing dam. This recharge is favoured by the preferential flow due to desiccation cracks in metallurgical waste. Geochemical modelling showed that potentially toxic heavy metals might exist largely in the forms of MSO₄^2– and M²⁺ in pore water of SAL metallurgical waste. All samples were supersaturated in goethite and hematite. Results from batch testing indicate that the heavy metals have two origins: natural, due to the existing ultramaphic rocks and laterites, and anthropogenic, by metallurgical waste rich in sulphate and (oxy)hydroxide minerals. These results highlight the need to locate and evaluate a new water source to supply the population of the city of Moa.     

Hydrogeochemistry and groundwater quality assessment of the multilayered aquifer in Lower Kelantan Basin,Kelantan, Malaysia

Continual expansion of population density, urbanization, agriculture, and industry in most parts of the world has increased the generation of pollution, which contributes to the deterioration of surface water quality. This causes the dependence on groundwater sources for their daily needs to accumulate day by day, which raises concerns about their quality and hydrogeochemistry. This study was carried out to increase understanding of the geological setup and assess the groundwater hydrogeochemical characteristics of the multilayered aquifers in Lower Kelantan Basin. Based on lithological data correlation of exploration wells, the study area can be divided into three main aquifers: shallow, intermediate and deep aquifers. From these three aquifers, 101 groundwater samples were collected and analyzed for various parameters. The results showed that pH values in the shallow, intermediate and deep aquifers were generally acidic to slightly alkaline. The sequences of major cations and anions were Na⁺ > Ca²⁺ > Mg²⁺ > K⁺ and HCO₃^? > Cl^? > SO₄^2? > CO₃^2?, respectively. In the intermediate aquifer, the influence of ancient seawater was the primary factor that contributed to the elevated values of electrical conductivity (EC), Cl^? and total dissolved solids (TDS). The main facies in the shallow aquifer were Ca–HCO₃ and Na–HCO₃ water types. The water types were dominated by Na–Cl and Na–HCO₃ in the intermediate aquifer and by Na–HCO₃ in the deep aquifer. The Gibbs diagram reveals that the majority of groundwater samples belonged to the deep aquifer and fell in the rock dominance zone. Shallow aquifer samples mostly fell in the rainfall zone, suggesting that this aquifer is affected by anthropogenic activities. In contrast, the results suggest that the deep aquifer is heavily influenced by natural processes.     

Geochemical and isotopic studies of groundwater conditions in the Densu River Basin of Ghana

The Densu River Basin (DRB) is an important agricultural area in Ghana and has a high population density. Water shortages have occurred in the basin due to drying out of surface water, heavy pollution and low yield in most of the production wells, which are crucial factors restricting sustainable socioeconomic development. This study was carried out to investigate the geochemical characteristics and evolution, as well as recharge processes in the DRB system with regard to the tectonics, geomorphology, lithology and flow system. It mainly used hydrochemistry, environmental isotopes and a series of comprehensive data interpretation, e.g., statistics, ionic ratios and Piper diagram to obtain a better understanding of the functioning of the system. The following hydrochemical processes were identified as the main factors controlling the water quality of the groundwater system: weathering of silicate minerals, dissolution, ion exchange and, to a lesser extent, evaporation, which seems to be more pronounced downgradient of the flow system. As groundwater flows from the recharge to discharge areas, chemical patterns evolve in the order of Ca²⁺–HCO₃ ^?, Ca²⁺/Mg²⁺–HCO₃ ^? to Ca²⁺/Na⁺–Cl^?, Ca²⁺–Na⁺–HCO₃ ^? and Na⁺–Cl^? according to lithology. The environmental isotope (δ¹⁸O, δ²H, ³H) measurements further revealed that groundwater in the DRB was a relatively well-mixed system as evidenced by the encoded narrow range of values. However, deviation from the rainwater signature indicates combined local processes such as direct percolation through preferential channels, evaporation, and probable surface water and anthropogenic contribution to the system.     

Application of hydrogeochemistry to uranium exploration in the pine creek geosyncline, northern territory, Australia

In the Pine Creek Geosyncline, fast moving, annually recharged, low-salinity ground waters dissolve uranium- and magnesium-enriched gangue minerals from mineralized aquifer rocks. The level of dissolved uranium depends on prevailing pH, Eh, salinity and degree of adsorption, which limits its effectiveness as an exploration indicator. Near each known deposit, leaching of magnesium-enriched gangue minerals produces ground waters with very similar major-element concentration plots, the shape of which constitutes a mineralized aquifer “signature”. Gangue minerals also supply high levels of Mg²⁺ (expressed as NMg = [Mg²⁺]/[Ca²⁺ + Mg²⁺ + Na⁺ + K⁺] in milliequivalents per litre) to contained ground waters, NMg > 0.8 being common in ground waters from mineralized aquifers at each Pine Creek Geosyncline deposit. Data from Ranger One No. 3 ore body illustrates how progressive mixing of waters from mineralized and unmineralized aquifers causes graded reductions in NMg, which, when plotted onto a ground plan, delineate a hydrogeochemical aureole.High NMg (> 0.8) coincides with high uranium concentration (> 20 μg/l of U) in ground waters near Nabarlek and Ranger. Because pH-Eh conditions in aquifers at Jabiluka depress uranium solution, < 10 μg/l of U is present, although NMg values are generally > 0.8. To date NMg has always been < 0.8 in nonmineralized aquifer waters, whereas uranium may be > 50 μg/l in ground waters from felsic igneous aquifers, which can be identified as uneconomic by low (< 0.4) NMg, and by a fixed relationship between uranium and co-leached species such as F^- and soluble salts.Measurements of pH, Eh, salinity, Fe(II), Ca, Mg, Na, K, Cl, SO₄, total carbonate, phosphate, F^-, Cu, Pb, Zn and U in waters from 48 percussion holes in and near the Koongarra ore bodies have been related to mineralogy recorded in drill logs. The composition of waters from 20 holes near and along strike from known mineralization, fitted the mineralized aquifer “signature”, had NMg > 0.8 and uranium up to 4100 μ/l. These data confirm the use in this region of NMg as a hydrogeochemical indicator of uranium mineralization; they also indicate additional zones of possible mineralization.     

Hydrogeochemistry and isotope techniques to determine water interactions in groundwater-dependent shallow lakes,Wet Pampa Plain,Argentina

This paper gives an account of the implementation of hydrochemical and isotopic techniques to identify and explain the processes that govern solute exchange in two groundwater-dependent shallow lakes in the Southeastern Pampa Plain of Argentina. Water samples (lakes, streams, spring water and groundwater) for hydrochemical and stable isotopic determination were collected and the main physical–chemical parameters were measured. The combination of stable isotope data with hydrogeochemical techniques was used for the identification of sources and preferential recharge areas to these aquatic ecosystems which allowed the explanation of the lake water origin. The hydrochemical processes which explain Los Padres Lake water chemistry are evaporation from groundwater, CO₂ input, calcite dissolution, Na⁺ release by Ca²⁺ and Mg²⁺ exchange, and sulfate reduction. The model that best aligns with La Brava Lake hydrochemical constraints includes: mixing, CO₂ and calcite dissolution, cationic exchange with Na⁺ release and Mg²⁺ adsorption, and to a lesser extent, Ca/Na exchange. This model suggests that the fractured aquifer contribution to this water body is greater than 50 %. An isotopic-specific fingerprint for each lake was identified, finding a higher evaporation rate for La Brava Lake compared to Los Padres Lake. Isotopic data demonstrate the importance of these shallow lakes as recharge areas to the regional aquifer, becoming areas of high groundwater vulnerability. The Tandilia Range System, considered in many hydrogeological studies as the impermeable bedrock of the Pampean aquifer, acts as a fissured aquifer in this area, contributing to low salinity waters and with a fingerprint similar to groundwater isotopic composition.     

Hydrochemical and isotopic characteristics of groundwater in the Souss Upstream Basin, southwestern Morocco

Heterogeneous shallow Plio-Quaternary formations of the Souss Plain represent the most important aquifer in southern High Atlas Mountains in Morocco. The present work was conducted in the Souss Upstream Basin to identify the chemical characteristics and the origin of groundwater in an aquifer under semi-arid climate. Isotopic and hydrochemical compositions combined with geological and hydrogeological data were used for this purpose. The total dissolved solids vary from 239 to 997 mg l⁻¹, and the following groundwater types are recognized: Ca²⁺–Mg²⁺–HCO₃⁻, Ca²⁺–Mg²⁺–SO₄²⁻ and Ca²⁺–Mg²⁺–Cl⁻. The groundwater is saturated and slightly supersaturated with respect to carbonate minerals and undersaturated with respect to evaporite minerals, which means that the groundwater composition is largely controlled by the dissolution of carbonate rocks known in the basin. The isotopic contents of groundwaters ranged from −8‰ to −5.2‰ for δ¹⁸O, from −52‰ to −34‰ for δD, and from 0 to 5.5 TU for tritium. The hydrogen (δD) and oxygen (δ¹⁸O) isotope signatures reveal a significant infiltration before evaporation takes place, indicating a major recharge directly from fractures in the crystalline and limestone formations of Atlas Mountains (above 800 m a.s.l.) and infiltration of surface water in the alluvial cones at the border of the Atlas basins. The very low tritium values suggest that the groundwater recharge follows a long flow path and a mixing between old and modern water is shown. However, a slight evaporation effect is noted in the southern part of the basin close to the Anti-Atlas Mountains.     

Geochemical evolution and timescale of seawater intrusion into the coastal aquifer of Israel

This study is an attempt to quantify the geochemical processes and the timescale of seawater intrusion into a coastal aquifer from changes in the major ionic composition of the water and the natural distribution of the cosmogenic isotopes ¹⁴C and ³H. For that purpose, we sampled saline and brackish groundwaters from the Israeli coastal aquifer. A multilayer sampler (MLS) was used to obtain very high resolution (10 cm) profiles across the fresh-saline water interface (FSI).The chemical and stable isotope data revealed three distinct water types (end members) that are located in different zones on the route to the coastal aquifer: (1) slightly modified Mediterranean seawater (SWS); (2) slightly diluted (with up to 20% fresh groundwater) saline groundwater (SDS); and (3) fresh groundwater (FGW).The SWS samples generally show an excess of total alkalinity and total dissolved inorganic carbon (DIC), and a depletion of ¹³C_DIC and ¹⁴C_DIC with respect to normal seawater indicating that anaerobic oxidation of organic matter is the first diagenetic reaction that affects seawater during its penetration into the bottom sediments. SDS waters appear when SWS is slightly diluted, gain Ca²⁺ and Sr²⁺, and is depleted in K⁺, suggesting that the main processes that transform SWS into SDS are slight dilution with fresh groundwater and cation exchange. At the fresh-saline water interface, SDS generally shows conservative mixing with FGW.Inspection of chemical data from coastal aquifers around the world indicates that intensive ion exchange in slightly diluted saline groundwater is a globally important phenomenon of seawater intrusion. Most of our saline groundwater samples contain substantial amounts of ³H suggesting that penetration of Mediterranean seawater and its inland travel to a distance of 50-100 m onshore occurred 15-30 yr ago. This is supported by the ¹⁴C_DIC mass balance that explains the relatively low ¹⁴C_DIC activities in the SDS as influenced by diagenesis and not by simple radioactive decay.     

Hydrogeochemical investigations and groundwater provinces of the Friuli Venezia Giulia Plain aquifers,northeastern Italy

Water resources are a key factor, particularly for the planning of the sustainable regional development of agriculture, as well as for socio-economic development in general. A hydrochemical investigation was conducted in the Friuli Venezia Giulia aquifer systems to identify groundwater evolution, recharge and extent of pollution. Temperature, pH, electric conductivity, total dissolved solids, alkalinity, total hardness, SAR, Ca²⁺, Na⁺, K⁺, Mg²⁺, Cl⁻, SO₄ ²⁻, NO₃ ⁻, HCO₃ ⁻ _, water quality and type, saturation indexes and the environmental stable isotope δ¹⁸O were determined in 149 sampling stations. The pattern of geochemical and oxygen stable isotope variations suggests that the sub-surface groundwater (from phreatic and shallow confined aquifers) is being recharged by modern precipitations and local river infiltrations. Four hydrogeological provinces have been recognised and mapped in the Friuli Venezia Giulia Plain having similar geochemical signatures. These provinces have different degrees of vulnerability to contamination. The deep confined groundwater samples are significantly less impacted by surface activities; and it appears that these important water resources have very low recharge rates and would, therefore, be severely impacted by overabstraction.     

Deciphering the interaction between quaternary and continental Sabkhas aquifers in Central Tunisia using hydrochemical and isotopic tools

Climate aridity and intensive exploitation due to uncontrolled pumping for irrigation have caused a drastic decrease in the piezometric level of the shallow aquifer of Chougafiya plain, central Tunisia, and have seriously degraded groundwater quality. According to the hydrochemical data (Cl^?, SO₄ ^2?, NO₃ ^?, HCO₃ ^?, Br^?, Na⁺, Mg²⁺, K⁺, Ca²⁺, Sr²⁺) and the stable isotopes (¹⁸O and ²H content), groundwater salinization in the investigated aquifer is caused by four main processes: (1) evaporite dissolution (2) cation exchange reactions (3) evaporation processes and (4) mixing with Sabkhas salt water causing salinity to increase in the central and southern parts of the basin. The radiogenic (³H) isotope data provided insight into the presence of significant contemporaneous recharge waters in the western part of the shallow aquifer. The movement of the tritiated water may have occurred according to the general flow path (NW–SE). When tritium was used in conjunction with the stable isotopes and chloride, the mixing process could be clearly identified, especially in the central part of the study area.