Investigation of groundwater mineralization in the Hammamet–Nabeul unconfined aquifer,north-eastern Tunisia: geochemical and isotopic approach

Detailed hydrogeochemical and isotopic data of groundwaters from the Hammamet–Nabeul unconfined aquifer are used to provide a better understanding of the natural and anthropogenic processes that control the groundwater mineralization as well as the sources of different groundwater bodies. It has been demonstrated that groundwaters, which show Na–Cl and Ca–SO₄–Cl water facies, are mainly influenced by the dissolution of evaporates, the dedolomitization and the cation-exchange process; and supplementary by anthropogenic process in relation with return flow of irrigation waters. The isotopic signatures permit to classify the studied groundwaters into two different groups. Non-evaporated groundwaters that are characterized by depleted δ ¹⁸O and δ ²H contents highlighting the importance of modern recharge at higher altitude. Evaporated groundwaters with enriched contents reflecting the significance infiltration of return flow irrigation waters. Tritium data in the studied groundwaters lend support to the existence of pre-1950 and post-1960 recharge. Carbon-14 activities in shallow wells that provide evidence to the large contamination by organic ¹⁴C corroborate the recent origin of the groundwaters in the study area.     

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.     

Geochemistry of heavily exploited aquifers in the Emilia-Romagna region (Po Valley, northern Italy)

 More than 5 800 chemical analyses on water samples collected during 1987–1995 from 528 monitoring wells located in the southernmost part of the Po Valley (Emilia-Romagna region, northern Italy), one of the most urbanized, industrialized and agriculturally developed areas of Italy, have been processed. The analysis of data showed that: (1) waters are discharging from both confined and unconfined aquifers; (2) the water in the unconfined aquifer(s) is Ca(Mg)-HCO₃ in composition while confined ones are Na-Cl and/or Na-(HCO₃); (3) both confined and unconfined aquifer samples have δ¹⁸O and δD isotopic values of meteoric signature; (4) waters from both the aquifers are at least 40 years old; (5) the pumping rate has caused subsidence, particularly where the aquifer(s) is (are) unconfined; (6) the unconfined aquifer(s) is exposed to the risk of NO₃ pollution; (7) considering the present "pressure" (i.e. pumping rate) on this natural environment by human activity, care must be taken in the future to preserve this "strategic" resource. Received: 27 October 1997 · Accepted: 12 March 1998     

Identifying sources of groundwater recharge in the Merguellil basin (Tunisia) using isotopic methods: implication of dam reservoir water accounting

Thirty-two groundwater samples collected from the Merguellil Wadi basin (central Tunisia) complemented by the Haouareb dam reservoir water samples have been isotopically analysed in order to investigate the implication of the reservoir water to recharging the aquifer, and also to infer the sources, relative ages and mixing processes in the aquifer system. Plots of the stable isotopes data against the local meteoric lines of Tunis-Carthage and Sfax indicate a strong implication of the dam water noticeable up to a distance of 6–7 km. A contribution as much as 80% of the pumped water has been evidenced using isotopic mass balance. In addition, poorly distinguished water clusters in the stable isotope plots, but clearly identified in the diagrams δ¹⁸O versus ³H and ³H versus ¹⁴C, indicate various water types related to sources and timing of recharge. The isotopic signatures of the dam accounting water, the “old” and “native” recharged waters, have been evidenced in relation to their geographical distribution and also to their radiogenic isotopes (³H and ¹⁴C) contents. In the south-western part of the aquifer, mixing process occurs between the dam reservoir water and both the “old” and “native” water components.     

Groundwater flow patterns in the San Luis Valley,Colorado, USA revisited: an evaluation of solute and isotopic data

Groundwater systems in the San Luis Valley, Colorado, USA have been re-evaluated by an analysis of solute and isotopic data. Existing stream, spring, and groundwater samples have been augmented with 154 solute and isotopic samples. Based on geochemical stratification, three groundwater regimes have been identified within 1,200 m of the surface: unconfined, upper active confined, and lower active confined with maximum TDS concentrations of 35,000, 3,500 and 600 mg/L, respectively. The elevated TDS of northern valley unconfined and upper active confined systems result from mineral dissolution, ion exchange and methanogenesis of organic and evaporate lake sediments deposited in an ancient lake, herein designated as Lake Sipapu. Chemical evolutions along flow paths were modeled with NETPATH. Groundwater ages, and δ¹³C, δ²H and δ¹⁸O compositions and distributions, suggest that mountain front recharge is the principle recharge mechanism for the upper and lower confined aquifers with travel times in the northern valley of more than 20,000 and 30,000 ¹⁴C years, respectively. Southern valley confined aquifer travel times are 5,000 ¹⁴C years or less. The unconfined aquifer contains appreciable modern recharge water and the contribution of confined aquifer water to the unconfined aquifer does not exceed 20%.     

Geochemistry and14C dating of groundwaters from Jurassic aquifers of North Aquitaine Basin (France)

Twenty-seven samples from a confined Lower-Middle Jurassic aquifer and an unconfined Oxfordian aquifer of the North Aquitaine Basin (France) have been analysed for their major elements, Br⁻,¹⁸O,²H,¹³C and¹⁴C contents. Hydrochemistry indicates (1) a dissolution of carbonate and anhydrite near the recharge zone and (2) a dilution of a saline water derived from a seawater/halite mixing in the deeper part of the aquifer. The mixing is also visible in a δ¹⁸O vs Cl⁻ diagram in which two different groups appear: recent waters and old waters indicating a mixing process between fresh and saline groundwaters. The composition of the saline water is likely to be 34,100±11,200 ppm in Cl, 70±20 ppm in Br and more than −3.5±07‰ vs SMOW in¹⁸O.¹³C contents indicate (1) a C exchange with CaCO₃ matrix for groundwaters near the recharge zone and (2) a participation of organic matter in the deep part of the aquifer.Residence times for waters near the area of the aquifer outcrop correspond to Holocene and Late Pleistocene periods. The depletion in stable isotopes of 10 to 15,000 y B.P. waters show a late glacial period infiltration to the aquifer. After a distance of about 10 km in the aquifer, the¹⁴C activities are 0 pmc showing the presence of ‘old’ groundwaters.     

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.     

Quantifying regional groundwater flow between Continental Intercalaire and Djeffara aquifers in southern Tunisia using isotope methods

Large-scale interaction between the Continental Intercalaire and the Djeffara aquifer systems in the southeast of Tunisia has been investigated with the aid of chemical and isotopic tracers. Two distinct groundwater types have been identified: (1) the Continental Intercalaire groundwater characterized by elevated temperatures (50–61.4°C), low δ¹⁸O (−8.4 to−7.87) and δ²H (−67.2 to−59) values and negligible radiocarbon content, both testifying its great age dating from the late Pleistocene period, and (2) the Djeffara groundwater with distinctly heavier isotopic composition (δ¹⁸O = −8.31 to −5.80, δ²H = −65.9 to −31.9). The Djeffara groundwaters reveal a distinct changes of physico-chemical and isotopic parameters near El Hamma Faults in the northwestern part of the Djeffara basin. These changes could possibly be explained by a vertical leakage from the Continental Intercalaire aquifer through El Hamma Faults. The mixing proportions inferred from stable isotope mass balance prove that the contribution of the Continental Intercalaire to the recharge of Djeffara aquifer is very significant and may reach 100% in the El Hamma region and in the northern part of Gabes. Isotope tracers strongly suggest that recent recharge to the Djeffara aquifer system is very limited. Its current yield, particularly in its central and northern parts can be maintained only thanks to large-scale underground inflow from the Continental Intercalaire aquifer system, which carries late Pleistocene palaeowater. Consequently, current exploitation of groundwater resources of the Djeffara aquifer has non-sustainable character.     

Recharge of the plio-quaternary water table aquifer in Tunisian chotts region estimated from stable isotopes

The hydrodynamic groundwater data and stable isotopes of water have been used jointly for better understanding of upward leakage and mixing processes in the Djerid aquifer system (southwestern Tunisia). The aquifer system is composed of the upper unconfined Plio-Quaternary (PQ) aquifer, the intermediate (semi-)confined Complex Terminal (CT) aquifer and the deeper confined Continental Intercalaire (CI) aquifer. A total of 41 groundwater samples from the CT and PQ aquifers were collected during June 2001. The stable isotope composition of waters establishes that the CT deep groundwater (depleted as compared to present Nefta local rainfall) is ancient water recharged during late Quaternary time. The relatively recent water in the shallow PQ aquifer is composed of mixed water resulting from upward leakage and sporadic meteoric recharge. In order to characterize the meteoric input signal for PQ in the study area, rainfall water samples were collected during 4 years (2000–2003) at the Nefta meteorological station. Weighted mean values of isotopic contents with respect to rainfall amounts have been computed. Despite the short collection period in the study area, results agree with those found in Beni Abbes (southwestern Algerian Sahara) by Fontes on 9 years of rainfall surveillance. Stable isotopic relationships provide clear evidence of shallow PQ aquifer replenishment by deep CT groundwater. The ¹⁸O/upward leakage rate allowed the identification of distinctive PQ waters related to CT aquifer configuration (confined in the western part of the study area, semi-permeable in the eastern part). These trends were confirmed by the relation ¹⁸O/TDS. The isotope balance model indicated a contribution of up to 75% of the deep CT groundwater to the upper PQ aquifer in the western study area, between Nefta and Hazoua.     

Groundwater recharge and flow in the Lower Cretaceous Nubian Sandstone aquifer in the Sinai Peninsula, using isotopic techniques and hydrochemistry

The present work was conducted in the Sinai Peninsula (1) to identify the recharge and flow characteristics and to evaluate the continuity of the Lower Cretaceous Nubian Sandstone aquifer; and (2) to provide information for the aquifer's rational appraisal. Isotopic and hydrochemical compositions combined with the geological and hydrogeological settings were used for this purpose. A considerable depletion in isotopic content (oxygen-18 and deuterium) and low d-excess values exist in the studied groundwater, reflecting the contribution of old meteoric water that recharged the aquifer in pluvial times. Modern recharge also occurs from precipitation that falls on the aquifer outcrops. The wide scatter of the data points around the two meteoric lines, the global meteoric water line (GMWL) and Mediterranean meteoric water line (MMWL), in the δ¹⁸O–δD diagram indicates considerable variation in recharge conditions (amount, altitude, temperature, air masses, distances from catchment, overland flow, etc.). The isotopic composition in the El-Bruk area is minimum (¹⁸O=–9.53‰), very close to the average value of the Western Desert Nubian Sandstone (¹⁸O=–10‰), where the local structural and lithologic conditions retard groundwater flow and the main bulk of water becomes noncyclic. The continuity of the aquifer in northern and central Sinai is evidenced by the isotopic similarity between samples taken from above and below the central Sinai Ragabet El-Naam fault, the distribution of potentiometric head, and hydrogeological cross sections. The combination of isotopic composition in terms of ¹⁸O and chemical composition in terms of TDS and salt contents is the basis for separating the studied groundwater into groups that reflect the recharge sources and isotopic and chemical modifications during flow. Electronic Publication     

Assessing groundwater availability and the response of the groundwater system to intensive exploitation in the North China Plain by analysis of long-term isotopic tracer data

The use of isotope tracers as a tool for assessing aquifer responses to intensive exploitation is demonstrated and used to attain a better understanding of the sustainability of intensively exploited aquifers in the North China Plain. Eleven well sites were selected that have long-term (years 1985–2014) analysis data of isotopic tracers. The stable isotopes δ¹⁸O and δ²H and hydrochemistry were used to understand the hydrodynamic responses of the aquifer system, including unconfined and confined aquifers, to groundwater abstraction. The time series data of ¹⁴C activity were also used to assess groundwater age, thereby contributing to an understanding of groundwater sustainability and aquifer depletion. Enrichment of the heavy oxygen isotope (¹⁸O) and elevated concentrations of chloride, sulfate, and nitrate were found in groundwater abstracted from the unconfined aquifer, which suggests that intensive exploitation might induce the potential for aquifer contamination. The time series data of ¹⁴C activity showed an increase of groundwater age with exploitation of the confined parts of the aquifer system, which indicates that a larger fraction of old water has been exploited over time, and that the groundwater from the deep aquifer has been mined. The current water demand exceeds the sustainable production capabilities of the aquifer system in the North China Plain. Some measures must be taken to ensure major cuts in groundwater withdrawals from the aquifers after a long period of depletion.     

Radiocarbon dating of dissolved inorganic carbon in groundwater from confined parts of the Upper Floridan aquifer, Florida, USA

Geochemical reaction models were evaluated to improve radiocarbon dating of dissolved inorganic carbon (DIC) in groundwater from confined parts of the Upper Floridan aquifer in central and northeastern Florida, USA. The predominant geochemical reactions affecting the ¹⁴C activity of DIC include (1) dissolution of dolomite and anhydrite with calcite precipitation (dedolomitization), (2) sulfate reduction accompanying microbial degradation of organic carbon, (3) recrystallization of calcite (isotopic exchange), and (4) mixing of fresh water with as much as 7% saline water in some coastal areas. The calculated cumulative net mineral transfers are negligibly small in upgradient parts of the aquifer and increase significantly in downgradient parts of the aquifer, reflecting, at least in part, upward leakage from the Lower Floridan aquifer and circulation that contacted middle confining units in the Floridan aquifer system. The adjusted radiocarbon ages are independent of flow path and represent travel times of water from the recharge area to the sample point in the aquifer. Downgradient from Polk City (adjusted age 1.7 ka) and Keystone Heights (adjusted age 0.4 ka), 14 of the 22 waters have adjusted ¹⁴C ages of 20–30 ka, indicating that most of the fresh-water resource in the Upper Floridan aquifer today was recharged during the last glacial period. All of the paleowaters are enriched in ¹⁸O and ²H relative to modern infiltration, with maximum enrichment in δ¹⁸O of approximately 2.0‰. Electronic Publication     

Study of shallow groundwater quality evolution under saline intrusion with environmental isotopes and geochemistry

Evolution of the shallow groundwater quality under saline intrusion in porous aquifer system has been studied with environmental isotopes and geochemistry in the Laizhou Bay area, China. Two campaigns of water sampling from various sources were carried out in spring and winter for environmental isotopic and chemical analyses. The origin of groundwater salinity from intrusion of both modern seawater and deep brine water was identified by analysing the correlations between ¹⁸O, D, T, Cl⁻, SO₄²⁻ and electrical conductivity. The results indicate that the brine is originated from evaporating and concentrating of intruded seawater and its δD and δ¹⁸O are different from modern seawater but similar to those of mixture of seawater with fresh groundwater. It is hard to distinguish the salinity origin in this area by the δD–δ¹⁸O relationship alone. The relations between δ¹⁸O and conductivity, Cl⁻ and SO₄²⁻ have been used to identify the salinity origin due to the distinct difference in salinity between the brine and seawater, conjunctively with use of T. A threshold of T = 12 TU was adopted to identify the origin of saline groundwater.     

Environmental isotopic and hydrochemical study of groundwater in the Ejina Basin,northwest China

The study investigates the groundwater evolution and its residence time in the Ejina Basin, northwest China according to isotope and hydrochemical analyses results. The groundwater chemistry is mainly controlled by the dissolution of halite, Glauber’s salt, gypsum, dolomite and calcite, also influenced by other processes such as evaporation, ion exchange, and deposition. Based on tritium content in atmospheric precipitation and by adopting a model with exponential time distribution function, the mean residence time of the unconfined aquifer groundwater with fairly high tritium activities (21–49 TU) is evaluated. The results show that these groundwaters have low residence time (5–120 years) and are renewable. In contrast, the deep confined groundwaters are tritium-free and radiocarbon values range from 18.3 to 26.7 pmc. According to the most commonly used ¹⁴C correction models, the radiocarbon groundwater ages were calculated which yield ages of approximately 4,087–9,364 years BP. Isotopic signatures indicate formation of deep confined groundwaters in a colder and wetter climate during the late Pleistocene and Holocene. It is suggested that long-term, rational water usage guide should be set up for the Heihe River Basin as a whole to permit a considerable discharge to the Ejina Basin.     

Groundwater flow system in Bengal Delta,Bangladesh revealed by environmental isotopes

A total number of 328 groundwater samples are analysed to evaluate the groundwater flow systems in Bengal Delta aquifers, Bangladesh using environmental isotope (²H, ¹⁸O, ¹³C, ³H, and ¹⁴C) techniques. A well-defined Local Meteoric Water Line (LMWL) δ²H = 7.7 δ¹⁸O + 10.7 ‰ is constructed applying linear correlation analyses to the monthly weighted rainfall isotopic compositions (δ¹⁸O and δ²H). The δ¹⁸O and δ²H concentrations of all groundwater samples in the study area are plotted more or less over the LMWL, which provides compelling evidence that all groundwaters are derived from rainfall and floodwater with a minor localized evaporation effects for the shallow groundwaters. Tritium concentration is observed in 40 samples out of 41 with values varying between 0.3 and 5.0 TU, which represents an evidence of young water recharge to the shallow and intermediate aquifers. A decreasing trend of ¹⁴C activity is associated with the heavier δ¹³C values, which indicates the presence of geochemical reactions affecting the ¹⁴C concentration along the groundwater flow system. Both vertical and lateral decrease of ¹⁴C activity toward down gradient show the presence of regional groundwater flow commencing from the unconfined aquifers, which discharges along the coastal regions. Finally, shallow, intermediate, and deep groundwater flow dynamics has revealed in the Bengal Delta aquifers, Bangladesh.     

Salinization of groundwater in the North German Basin: results from conjoint investigation of major, trace element and multi-isotope distribution

Conjoint consideration of distribution of major, rare earth elements (REE) and Y (combined to REY) and of H, O, C, S, Sr isotopes reveals that four types of groundwater are distinguishable by their chemical composition presented by spider patterns. REY patterns indicate thermo-saline deep water and two types of shallow saline groundwaters. Presence of connate waters is not detectable. Sr isotope ratios distinguish three sources of Sr: fast and slow weathering of biotite and K-feldspar in Pleistocene sediments, respectively, and dissolution of limestones. δ¹³C(DIC) indicate dissolution of limestone under closed and open system conditions. Numerous samples show δ¹³C(DIC) > 13‰ which is probably caused by incongruent dissolution of calcite and dolomite. The brines from below 1,000 m represent mixtures of pre-Pleistocene seawater or its evaporation brines and infiltrated post-Pleistocene precipitation. The shallow waters represent mixtures of Pleistocene and Recent precipitation salinized by dissolution of evaporites or by mixing with ascending brines. The distribution of water types is independent on geologic units and lithologies. Even the Tertiary Rupelian aquiclude does not prevent salinization of the upper aquifer.     

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 and isotopic study of groundwater in the Habor Lake Basin of the Ordos Plateau,NW China

Hydrogeochemistry and isotopes were used to understand the origin and geochemical evolution in the Habor Lake Basin, northwestern China. Groundwater samples were taken, and the isotopic compositions δD, δ¹⁸O and major ions were analyzed. The groundwater can be divided into three types: the Quaternary groundwater, the shallow Cretaceous groundwater and the deep Cretaceous groundwater. The groundwater chemistry is mainly controlled by the feldspar weathering and dolomite weathering, the dissolution of Glauber’s salt, and cation exchange. Chemistry of lake water is mainly controlled by evaporation and precipitation. The stable isotopes of oxygen and hydrogen in groundwater cluster along the local meteoric water line, indicating that groundwater is of meteoric origin. Comparing with shallow groundwater, deep groundwater is depleted in heavy isotopes indicating that deep groundwater was recharged during late Pleistocene and Holocene, during which the climate was more wetter and colder than today.     

Hydrochemistry of urban groundwater in Seoul, South Korea: effects of land-use and pollutant recharge

The ionic and isotopic compositions (δD, δ¹⁸O, and ³H) of urban groundwaters have been monitored in Seoul to examine the water quality in relation to land-use. High tritium contents (6.1–12.0 TU) and the absence of spatial/seasonal change of O–H isotope data indicate that groundwaters are well mixed within aquifers with recently recharged waters of high contamination susceptibility. Statistical analyses show a spatial variation of major ions in relation to land-use type. The major ion concentrations tend to increase with anthropogenic contamination, due to the local pollutants recharge. The TDS concentration appears to be a useful contamination indicator, as it generally increases by the order of forested green zone (average 151 mg/l), agricultural area, residential area, traffic area, and industrialized area (average 585 mg/l). With the increased anthropogenic contamination, the groundwater chemistry changes from a Ca–HCO₃ type toward a Ca–Cl(+NO₃) type. The source and behavior of major ions are discussed and the hydrochemical backgrounds are proposed as the basis of a groundwater management plan.     

Geochemical and stable isotopic evolution of the Guarani Aquifer System in the state of São Paulo, Brazil

The purpose of this report is to explain geochemical and stable isotopes trends in the Brazilian unit of the Guarani Aquifer System (Botucatu and Piramboia aquifers) in S?o Paulo State, Brazil. Trends of dissolved species concentrations and geochemical modeling indicated a significant role of cation exchange and dissolution of carbonates in downgradient evolution of groundwater chemistry. Loss of calcium by the exchange for sodium drives dissolution of carbonates and results in Na–HCO₃ type of groundwater. The cation-exchange front moves downgradient at probably much slower rate compared to the velocity of groundwater flow and at present is located near to the cities of Sert?ozinho and águas de Santa Barbara (wells PZ-34 and PZ-148, respectively) in a shallow confined area, 50–70 km from the recharge zone. Part of the sodium probably enters the Guarani Aquifer System. together with chloride and sulfate from the underlying Piramboia Formation by diffusion related to the dissolution of evaporates like halite and gypsum. High concentrations of fluorine (up to 13.3 mg/L) can be explained by dissolution of mineral fluoride also driven by cation exchange. However, it is unclear if the dissolution takes place directly in the Guarani Aquifer System or in the overlying basaltic Serra Geral Formation. There is depletion in δ ²H and δ ¹⁸O values in groundwater downgradient. Values of δ ¹³C(DIC) are enriched downgradient, indicating dissolution of calcite under closed system conditions. Values of δ ¹³C(DIC) in deep geothermal wells are very high (>–6.0‰) and probably indicate isotopic exchange with carbonates with δ ¹³C about –3.0‰. Future work should be based on evaluation of vertical fluxes and potential for penetration of contamination to the Guarani Aquifer System. Electronic Publication