Deciphering interaction of regional aquifers in Southern Tunisia using hydrochemistry and isotopic tools

Groundwater is the most important source of water supply in southern Tunisia. Previous hydrogeologic and isotopic studies carried out in this region revealed the existence of two major aquifer systems: the “Complex Terminal” (CT) and the “Continental Intercalaire” (CI). Turonian carbonates constitute one of the major aquifer levels of the CT multilayered aquifer. It extends over most of southern Tunisia, and its hydrodynamic regime is largely influenced by tectonics, lithology and recharge conditions. Forty-eight groundwater samples from the CI and Turonian aquifers were collected between January and April 2004 for chemical and isotopic analyses. Hydrochemistry and isotopic tools were combined to get an insight into the processes controlling chemical composition of groundwater and wide-scale interaction of these two aquifer systems. Analysis of the dissolved constituents revealed that several processes control the observed chemical composition: (i) incongruent dissolution of carbonate minerals, (ii) dissolution of evaporitic minerals, and (iii) cation exchange. Dissolution alone cannot account for the observed high supersaturation states of groundwater with respect to calcite and dolomite. The observed supersaturation is most probably linked to geogenic CO₂ entering water-bearing horizons of the CT and CI aquifers via deep tectonic faults and discontinuities and subsequent degassing in the exploitation wells. Presence of geogenic CO₂ in the investigated region was confirmed by C isotope data of the DIC reservoir. The radiocarbon content of the Turonian samples varied between 9.5 and 43 pmc. For CI samples generally lower values were recorded, between 3.8 and 22.5 pmc. Stable isotope composition of Turonian groundwater samples varied from −8.3 to −5.3‰ for δ¹⁸O and from −60 to −25‰ for δ²H. The corresponding ranges of δ values for the Continental Intercalaire samples were from −8.9‰ to −6.9‰ for δ¹⁸O and from −68.2‰ to −45.7‰ for δ²H. Stable isotope composition of groundwater representing CT and CI aquifers provide strong evidence for regional interaction between both systems.     

Recharge,geochemical processes and water quality in karst aquifers: Central West Bank,Palestine

The Central West Bank aquifer (CWB) is one of the most important resources of fresh groundwater of Palestine. The geology of the area consists mainly of karstic and permeable limestones and dolomites interbedded with argillaceous beds of late Albian–Turonian age. Exploitation of the CWB aquifer, combined with lack of information required to understand the groundwater pattern, represents a challenge for reservoir management. The present work reports hydrogeochemistry, microbiology and environmental isotope data from spring water samples, which were utilized to understand recharge mechanisms, geochemical evolution and renewability of groundwater in CWB aquifer. Besides the major chemical compositions, ionic ratios were used to delineate mineral-solution reactions and weathering processes. Interpretation of chemical data suggests that the chemical evolution of groundwater is primarily controlled by (1) water–rock interactions, involving dissolution of carbonate minerals (calcite and dolomite), and (2) cation exchange processes. The measured equation of the local meteoric water line is δD?=?5.8 δ¹⁸O?+?9.9. Stable isotopes show that precipitation is the source of recharge to the groundwater system. The evaporation line has a linear increasing trend from south to north direction in the study area. All analyzed spring waters are suitable for irrigation, but not for drinking purposes. The results from this study can serve as a basis for decision-makers and stakeholders, with the intention to increase the understanding of sustainable management of the CWBs.     

Hydrogeochemistry of groundwaters in a semi-arid region. El Ma El Abiod aquifer, Eastern Algeria

In this work, we present results of the hydrogeochemical and isotopic studies on groundwater samples from the El Ma El Abiod Sandstone aquifer, in Tébessa, Algeria. Chemical and environmental isotope data are presented and discussed in order to identify the geochemical processes and their relation with groundwater quality as well as to get an insight into the hydrochemical evaluation, in space and time, of groundwater and of the origin of dissolved species. A combined hydrogeologic and isotopic investigation have been carried out using chemical and isotopic data to deduce a hydrochemical evaluation of the aquifer system based on the ionic constituents, water types, hydrochemical facies, and factors controlling groundwater quality. All of the investigated groundwaters are categorized into two chemical types: low mineralized water type and relatively high mineralized water type. Interpretation of chemical data, based on thermodynamic calculations and geochemical reaction models of selected water groups constructed using PHREEQC, suggest that the chemical evolution of groundwater is primarily controlled by water–rock interactions, involving (1) acidic weathering of aluminosilicates, (2) dissolution of secondary carbonate minerals, and (3) cation exchange of Na⁺ for Ca²⁺. However, the original composition of groundwater may have been modified by further secondary processes such as mixing of chemically different water masses. The combined use of SI and mass-balance modeling has shown to be a useful approach in interpreting groundwater hydrochemistry in an area where large uncertainties exist in the understanding of the groundwater flow system. Interpretation of ¹⁸O and ²H, suggest that the recharge of the investigated groundwaters may result from different mechanisms.     

Characterization of surface water and groundwater in the Damascus Ghotta basin: hydrochemical and environmental isotopes approaches

The hydrochemistry of major ions and environmental isotope compositions (¹⁸O, ²H and tritium) of water samples have been used to investigate the characteristics of rainfalls, surface water and groundwater in the Damascus Ghotta basin. The groundwater salinity in the Damascus Ghotta basin gradually increases, as the groundwater moves from western to south-eastern and north-eastern parts of the basin. A strong relationship exists between the Barada river and the surrounded groundwaters, mainly in terms of recharge by infiltration of surface waters. The groundwater quality in the Adra region has clearly become less saline as a result of establishment of the sewage-water-treatment station in this area since 1997. The uncommon depleted stable isotope concentrations in the vicinity of Al-Ateibeh Lake and Adra valley could be interpreted as a result of sub-flow recharge from the Cenomanian–Turonian aquifer, mostly prolonged along the Damascus Fault, which forms direct contact between this complex and the Quaternary alluvium aquifers. The extensive exploitation of water from the Cenomanian–Turonian aquifer for drinking water supply would shortly be reflected by a gradual decline of the groundwater table in the Damascus Ghotta basin. Amelioration of water quality in the Damascus basin still requires further management strategies and efforts to be taken within the forthcoming years.     

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.     

Hydrogeochemical and Isotopic Study of Groundwater in a Semi-arid Region: Yeniceoba Plain (Cihanbeyli-KONYA), Central Anatolia,Turkey

Groundwater is the most important source of water supply in the Yeniceoba Plain in Central Anatolia,Turkey.An understanding of the geochemical evolution of groundwater is important for the sustainable development of water resources in this region.A hydrogeochemical investigation was conducted in the Plio-Quaternary aquifer system using stable isotopes(δ~(18)O andδD),tritium(~3H),major and minor elements(Ca,Na,K,Mg,Cl,SO_4,NO_3,HCO_3 and Br)in order to identify groundwater chemistry patterns and the processes affecting groundwater mineralization in this system.The chemical data reveal that the chemical composition of groundwater in this aquifer system is mainly controlled by rock/water interactions including dissolution of evaporitic minerals,weathering of silicates,precipitation/dissolution of carbonates,ion exchange,and evaporation.Based on the values of Cl/Br ratio(300 mg/l)in the Plio-Quaternary groundwater,dissolution of evaporitic minerals in aquifer contributes significantly to the high mineralization.The stable isotope analyses indicate that the groundwater in the system was influenced by evaporation of rainfall during infiltration.Low tritium values(generally1 tritium units)of groundwater reflect a minor contribution of recent recharge and groundwater residence times of more than three or four decades.     

Desalination of a sedimentary rock aquifer system invaded by Pleistocene Champlain Sea water and processes controlling groundwater geochemistry

The objective of this study was to identify geochemical processes and Quaternary geological events responsible for the variations in groundwater geochemistry observed in a sedimentary rock aquifer system, including brackish to saline groundwater. Inorganic constituents and environmental isotopes were analyzed for 146 groundwater samples. Dissolution of carbonates dominates in recharge areas, resulting in Ca-, Mg-HCO₃ groundwater. Further along flow paths, under confined conditions, Ca²⁺–Na⁺ ion exchange causes groundwater evolution to Na-HCO₃ type. Na-Cl groundwater is also found and it falls on a seawater mixing line. Using conservative tracers, Cl⁻ and Br⁻, the original Champlain Sea water is shown to have been, in the region, a mixture of about 34% seawater and 66% freshwater, a composition still retained by some groundwater. Na-Cl groundwater thus results from mixing with former Champlain Sea water and also from solute diffusion from overlying marine clay. The system is thus found to be at different stages of desalinization, from the original Champlain Sea water still present in hydraulically stagnant areas of the aquifer to fully flushed conditions in parts, where more flow occurs, especially in recharge zones. The geochemical processes are integrated within the hydrogeological context to produce a conceptual geochemical evolution model for groundwater of the aquifer system.     

Multivariate statistical analysis of chemical and stable isotopic data as indicative of groundwater evolution with reduced exploitation

Groundwater resources in the North China Plain (NCP) are undergoing tremendous changes in response to the operation of groundwater exploitation reduction (GWER) project. To identify groundwater evolution in this complex context, hierarchical cluster analysis (HCA) and principal component analysis (PCA) were combined to interpret an integrated dataset of stable isotopes and chemical data from four sampling campaigns in a pilot area of groundwater control. We proposed a novel HCA approach integrating stable isotopes and chemical signals, which successfully partitioned the groundwater samples into the unconfined and the confined water samples. Stable isotopic evidence showed that the lateral inflow and the surface water may contribute more to groundwater recharge in this region than local modern precipitation. The unconfined water’s main hydrochemical types were Na type with mixed anions, and Na–Cl–SO₄ type, while the confined water was mainly Na–Cl and Na–SO₄ types. Geochemical processes mainly involved the dissolution/precipitation of halite, gypsum, Glauber's salt, feldspar, calcite and dolomite, as well as the cation exchange. PCA results showed that water–rock interaction (i.e., salinity-based and alkalinity-based processes) predominated the hydrochemical evolution, along with local nitrate contamination resulting from fertilizers and domestic sewage. The GWER project regulated the natural evolution of unconfined water chemistry, and significantly reduced the unconfined water’s salinity (mainly Na⁺, Mg²⁺, SO₄^2?). This may be attributed to upward leakage from low-salinity confined water at some parts of the aquifer. Additionally, insignificant changes in the confined water’s salinity reflected that the impact of GWER on the confined aquifer was negligible. This study facilitates the groundwater classification effectively in the areas lack of geological data, and enhances the knowledge of groundwater chemical evolution in such a region where groundwater restoration is in progress, with important implications for groundwater sustainable management in similar basins worldwide.     

Suitability assessment of deep groundwater for drinking and irrigation use in the Djeffara aquifers (Northern Gabes,south-eastern Tunisia)

The multilayered Djeffara aquifer system, south-eastern Tunisia, has been intensively used as a primary source to meet the growing needs of the various sectors (drinking, agricultural and industrial purposes). The analysis of groundwater chemical characteristics provides much important information useful in water resources management. Detailed knowledge of the geochemical evolution of groundwater and assessing the water quality status for special use are the main objective of any water monitoring study. An attempt has been made for the first time in this region to characterize aquifer behavior and appreciate the quality and/or the suitability of groundwater for drinking and irrigation purposes. In order to attend this objective, a total of 54 groundwater samples were collected and analyzed during January 2008 for the major cations (sodium, calcium, magnesium and potassium), anions (chloride, sulfate, bicarbonate), trace elements (boron, strontium and fluoride), and physicochemical parameters (temperature, pH, total dissolved salts and electrical conductivity). The evolution of chemical composition of groundwater from recharge areas to discharge areas is characterized by increasing sodium, chloride and sulfate contents as a result of leaching of evaporite rock. In this study, three distinct chemical trends in groundwater were identified. The major reactions responsible for the chemical evolution of groundwater in the investigated area fall into three categories: (1) calcite precipitation, (2) gypsum and halite dissolution, and (3) ion exchange. Based on the physicochemical analyses, irrigation quality parameters such as sodium absorption ratio (SAR), percentage of sodium, residual sodium carbonate, residual sodium bicarbonate, and permeability index (PI) were calculated. In addition, groundwater quality maps were elabortaed using the geographic information system to delineate spatial variation in physico-chemical characteristics of the groundwater samples. The integration of various dataset indicates that the groundwater of the Djeffara aquifers of the northern Gabes is generally very hard, brackish and high to very high saline and alkaline in nature. The water suitability for drinking and irrigation purposes was evaluated by comparing the values of different water quality parameters with World Health Organization (WHO) guideline values for drinking water. Piper trilinear diagram was constructed to identify groundwater groups where the relative major anionic and cationic concentrations are expressed in percentage of the milliequivalent per liter (meq/l), and it was demonstrated that the majority of the samples belongs to SO₄–Cl–Ca–Na, Cl–SO₄–Na–Ca and Na–Cl hydrochemical facies. As a whole, all the analyzed waters from this groundwater have revealed that this water is unsuitable for drinking purposes when comparing to the drinking water standards. Salinity, high electric conductivity, sodium adsorption ratio and sodium percentages indicate that most of the groundwater samples are inappropriate for irrigation. The SAR vary from medium (S2) to very high (S4) sodicity. Therefore, the water of the Djeffara aquifers of the northern Gabes is dominantly of the C4–S2 class representing 61.23 % of the total wells followed by C4–S3 and C4–S4 classes at 27.27 and 11.5 % of the wells, respectively. Based on the US Salinity Classification, most of the groundwater is unsuitable for irrigation due to its high salt content, unless certain measures for salinity control are undertaken.     

The recharge of glacial meltwater and its influence on the geochemical evolution of groundwater in the Ordovician-Cambrian aquifer system,northern part of the Baltic Artesian Basin

The geochemical evolution of groundwater in the Ordovician-Cambrian aquifer system in the northern part of the Baltic Artesian Basin (BAB) illustrates how continental glaciations have influenced groundwater systems in proglacial areas. The aquifer system contains water that has originated from various end-members: recent meteoric water, glacial meltwater and relict Na-Cl brine. The saline formation water that occupied the aquifer system prior to the glacial meltwater intrusion has been diluted by meltwaters of advancing-retreating ice sheets. The diversity in the origin of groundwater in the aquifer system is illustrated by a wide variety in δ¹⁸O values that range from −11‰ to −22.5‰. These values are mostly depleted with respect to values found in modern precipitation in the area. The chemical and isotopic composition of groundwater has been influenced by mixing between waters originating from different end-members. In addition, the freshening of a previously saline water aquifer due to glacial meltwater intrusion has initiated various types of water-rock interaction (e.g. ion exchange, carbonate mineral dissolution).     

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.     

Hydrogeochemical characteristics prediction using multiple linear regression: case study on unconfined aquifer in northeastern Tunisia

The main factors and mechanisms controlling the groundwater chemistry and mineralization are recognized through hydrochemical data. However, water quality prediction remains a key parameter for groundwater resources management and planning. The geochemical study of groundwater of a multilayered aquifer system in Tunisia is recognized by measurements of the pH, EC, total dissolved solids (TDS), major ion concentration and nitrates of 36 samples from pumping wells covering the aquifer extension and analyzed using standard laboratory and field methods. The calcite precipitation, gypsum, anhydrite and halite dissolution, and direct and reverse ion exchange are the principal process of chemical evolution in the Nadhour-Saouaf aquifer system. Using stepwise regression, the concentration groups of (Ca, Cl, and NO₃), (Cl, SO₄, and Mg), and (Ca and Na) exhibit significant prediction of TDS in Plio-Quaternary, Miocene, and Oligocene aquifer levels, respectively. The highest values of R ² and adjusted R ² close to 1 revealed the accuracy of the developed models which is confirmed by the weak difference between the measured and estimated values varying between ?12 and 8%. The important uncertainty parameters that affected the estimated TDS are assessed by the sensitivity analysis method. The concentration of (Cl), (Ca and Cl), and (Na) are the major parameters affecting the TDS sensitivity of the Plio-Quaternary, Miocene, and Oligocene aquifer levels, respectively. Hence, the developed TDS models provide a more simple and easy alternative to other methods used for groundwater quality estimation and prediction as proven from external validation on groundwater samples unconsidered in the model construction.     

Using 87Sr/86Sr, δ18O and δ2H isotopes along with major chemical composition to assess groundwater salinization in lower Shire valley,Malawi

Groundwater resources in some parts of the lower section of Shire River valley, Malawi, are not useable for rural domestic water supply due to high salinity. In this study, a combined assessment of isotopic (⁸⁷Sr/⁸⁶Sr, δ¹⁸O and δ²H) and major ion composition was conducted in order to identify the hydro-geochemical evolution of the groundwater and thereby the causes of salinity. Three major end-members (representing fresh- and saline groundwater, and evaporated recharge) were identified based on major ion and isotopic composition. The saline groundwater is inferred to result from dissolution of evaporitic salts (halite) and the fresh groundwater shows influence of silicate weathering. Conservative mixing models show that brackish groundwater samples result from a three component mixture comprising the identified end-members. Hence their salinity is interpreted to result from mixing of fresh groundwater with evaporated recharge and saline groundwater. On the other hand, the groundwater with low TDS, found at some distance from areas of high salinity, is influenced by mixing of evaporated recharge and fresh groundwater only. Close to the Shire marshes, where there is shallow groundwater, composition of stable isotopes of water indicates that evaporation may also be an important factor.     

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.     

Geochemical evolution of groundwater in southern Bengal Basin: The example of Rajarhat and adjoining areas,West Bengal,India

Detailed geochemical analysis of groundwater beneath 1223 km² area in southern Bengal Basin along with statistical analysis on the chemical data was attempted, to develop a better understanding of the geochemical processes that control the groundwater evolution in the deltaic aquifer of the region. Groundwater is categorized into three types: ‘excellent’, ‘good’ and ‘poor’ and seven hydrochemical facies are assigned to three broad types: ‘fresh’, ‘mixed’ and ‘brackish’ waters. The ‘fresh’ water type dominated with sodium indicates active flushing of the aquifer, whereas chloride-rich ‘brackish’ groundwater represents freshening of modified connate water. The ‘mixed’ type groundwater has possibly evolved due to hydraulic mixing of ‘fresh’ and ‘brackish’ waters. Enrichment of major ions in groundwater is due to weathering of feldspathic and ferro-magnesian minerals by percolating water. The groundwater of Rajarhat New Town (RNT) and adjacent areas in the north and southeast is contaminated with arsenic. Current-pumping may induce more arsenic to flow into the aquifers of RNT and Kolkata cities. Future large-scale pumping of groundwater beneath RNT can modify the hydrological system, which may transport arsenic and low quality water from adjacent aquifers to presently unpolluted aquifer.     

Geochemical and isotopic characterization of groundwater from shallow and deep limestone aquifers system of Aleppo basin (north Syria)

Stable isotopes (δ¹⁸O, δ²H and ¹³C) and radioactivity (³H, ¹⁴C) have been used in conjunction with chemical data to evaluate the processes generating the chemical composition, reconstruct the origin of the water and groundwater residence time. The Aleppo basin is comprised of two main limestone aquifers: the first one is unconfined of Paleogene age and the second is confined of Upper Cretaceous age. The chemical data indicate that the dissolution of minerals and evaporation are the main processes controlling groundwater mineralization. The groundwater from the two aquifers is characterized by distinctive stable isotope signatures. This difference in water isotopes is interpreted in terms of difference origin and recharge period. Fresh and brackish shallow groundwater were mostly recharged during the Holocene period. The presence of ³H in several groundwater samples of this aquifer gives evidence that groundwater recharge is going on. Brackish water of the deep confined aquifer has depleted stable isotope composition and very low ¹⁴C activity that indicates recharge during the late Pleistocene cold period.     

Saltwater intrusion and nitrate pollution in the coastal aquifer of Dar es Salaam, Tanzania

Dar es Salaam Quaternary coastal aquifer is a major source of water supply in Dar es Salaam City used for domestic, agricultural, and industrial uses. However, groundwater overdraft and contamination are the major problems affecting the aquifer system. This study aims to define the principal hydrogeochemical processes controlling groundwater quality in the coastal strip of Dar es Salaam and to investigate whether the threats of seawater intrusion and pollution are influencing groundwater quality. Major cations and anions analysed in 134 groundwater samples reveal that groundwater is mainly affected by four factors: dissolution of calcite and dolomite, weathering of silicate minerals, seawater intrusion due to aquifer overexploitation, and nitrate pollution mainly caused by the use of pit latrines and septic tanks. High enrichment of Na⁺ and Cl^? near the coast gives an indication of seawater intrusion into the aquifer as also supported from the Na–Cl signature on the Piper diagram. The boreholes close to the coast have much higher Na/Cl molar ratios than the boreholes located further inland. The dissolution of calcite and dolomite in recharge areas results in Ca–HCO₃ and Ca–Mg–HCO₃ groundwater types. Further along flow paths, Ca²⁺ and Na⁺ ion exchange causes groundwater evolution to Na–HCO₃ type. From the PHREEQC simulation model, it appears that groundwater is undersaturated to slightly oversaturated with respect to the calcite and dolomite minerals. The results of this study provide important information required for the protection of the aquifer system.     

Interaction between deep and shallow groundwater systems in areas affected by Quaternary tectonics (Central Italy): a geochemical and isotope approach

Hydro- and isotope geochemistry are used to refine groundwater conceptual models in two areas of central Italy (Acque Albule Basin and Velino River Valley) affected by extensional Quaternary tectonics, where deep and shallow groundwater flow systems are interacting. The role of geology, of recent deposits filling the plains and of main tectonic features controlling groundwater flowpaths and deep-seated fluids emergences are investigated and discussed. Environmental isotopes (²H and ¹⁸O) confirm recharge in the surrounding carbonate aquifers, and meteoric origin of both shallow and deep groundwater. Major ion chemistry indicates a mixing between shallow Ca-HCO₃ groundwater from carbonate aquifers and deep Ca-HCO₃-SO₄ groundwater, characterised by higher salinity and temperature and high concentration in sulphates. Isotopic composition of dissolved sulphates (δ ³⁴S and δ ¹⁸O) and dissolved inorganic carbon (δ ¹³C), henceforth indicated as DIC, are used to verify the presence of different sources of groundwater, and to validate the mixing model suggested by the major ion analyses. Sulphate isotope composition suggests a marine origin for the groundwater characterised by elevated sulphate concentration, whose source is present in the deep buried sequences. Carbon isotope composition confirms the role of a DIC source associated to CO₂ degassing of a deep reservoir. Groundwater conceptual models are improved underlining the importance of Plio-Pleistocene sequences filling the tectonic depression. In the Acque Albule area, the travertine plateau represents a mixing stratified aquifer, where deep groundwater contribution is spread into the shallow aquifer. The alluvial–clastic–lacustrine leaky aquifer of Velino Valley enables a complete mixing of shallow and deep groundwater allowing spot-located discharge of deep groundwater along tectonic patterns and facilitating sulphate reduction in the lacustrine sediments, explaining locally the presence of H₂S.     

Carbonate and carbon isotopic evolution of groundwater contaminated by produced water brine with hydrocarbons

The major ionic and dissolved inorganic carbon (DIC) concentrations and the stable carbon isotope composition of DIC (δ¹³C_DIC) were measured in a freshwater aquifer contaminated by produced water brine with petroleum hydrocarbons. Our aim was to determine the effects of produced water brine contamination on the carbonate evolution of groundwater. The groundwater was characterized by three distinct anion facies: HCO₃⁻-rich, SO₄²⁻-rich and Cl⁻-rich. The HCO₃⁻-rich groundwater is undergoing closed system carbonate evolution from soil CO_2(g) and weathering of aquifer carbonates. The SO₄²⁻-rich groundwater evolves from gypsum induced dedolomitization and pyrite oxidation. The Cl⁻-rich groundwater is contaminated by produced water brine and undergoes common ion induced carbonate precipitation. The δ¹³C_DIC of the HCO₃⁻-rich groundwater was controlled by nearly equal contribution of carbon from soil CO_2(g) and the aquifer carbonates, such that the δ¹³C of carbon added to the groundwater was −11.6‰. In the SO₄²⁻-rich groundwater, gypsum induced dedolomitization increased the ¹³C such that the δ¹³C of carbon added to the groundwater was −9.4‰. In the produced water brine contaminated Cl⁻-rich groundwater, common ion induced precipitation of calcite depleted the ¹³C such that the δ¹³C of carbon added to the groundwater was −12.7‰. The results of this study demonstrate that produced water brine contamination of fresh groundwater in carbonate aquifers alters the carbonate and carbon isotopic evolution.     

Impact of rock-water interactions and recharge on water resources quality of the Agadir-Essaouira basin,southwestern Morocco

The Agadir-Essaouira area in the occidental High Atlas Mountains of Morocco is characterized by a semi-arid climate. The scarcity and quality of water resources, exacerbated by long drought periods, constitute a major problem for a sustainable development of this region. Groundwater resources of carbonate units within Jurassic and Cretaceous aquifers are requested for drinking and irrigation purposes. In this study, we collected 84 samples from wells, boreholes, springs, and rivers. Hydrochemical and isotopic data were used to examine the mineralization and origin of water, which control groundwater quality. The chemical composition of water seems to be controlled by water-rock interactions, such as dissolution of carbonates (calcite and dolomite), weathering of gypsum, as well as ion exchange processes, which explain the observed variability. Stable isotopes results show that groundwater from the mainly marly Cretaceous aquifer are submitted to an evaporation effect, while samples from the chiefly calcareous Jurassic aquifer indicate a meteoric origin, due to a rapid infiltration of recharge runoff through the karstic outcrops. The low values of δ¹⁸O and δ²H suggest a local recharge from areas with elevations ranging from 400 to 1200 m for the Cretaceous aquifer and from 800 to 1500 m for the Jurassic units.