The inter-relationship between coastal sub-aquifers and the Mediterranean Sea, deduced from radioactive isotopes analysis

Radioactive isotopes were used to estimate the rate of seawater intrusion into the coastal aquifer of Israel, the connection between the different sub-aquifers, and the connection between the sub-aquifers and the sea. This was done by dating both fresh and saline groundwaters from the vicinity of the shoreline, which were analyzed for their ¹⁴C and tritium content together with their chemical and stable isotope composition. The results indicate that the distinct sub-aquifers differ in their water chemistry and age. The saline groundwater in the lower sub-aquifers is older than ca. 10,000 years, as evidenced by the absence of tritium and low ¹⁴C activity (<12 PMC). On the other hand, saline groundwaters in the upper sub-aquifers contain tritium and are thus younger than 50 years, indicating recent intrusion of seawater. The ages of the saline groundwaters become younger upward from the lower sub-aquifers to the upper ones, reflecting the sea-level rise since the last glacial period. The older ages also imply slow groundwater flow in the lower sub-aquifers. The fresh groundwaters in most cases in the lower sub-aquifers were found to be older than ca. 10,000 years and this implies that the flow to the sea is blocked or restricted.     

高放废物处置库北山预选区地下水同位素组成特征及其意义

在高放废物处置库选址中,场地水文地质条件的认识极为重要,因为任何从处置库释放出来的放射性物质都将通过地下水搬运向人类生存环境或生物圈迁移.甘肃北山地区是我国高放废物处置库的重要预选区之一,位于我国西北甘肃省西北部.为了认识预选区的水文地质条件,从水文地质角度评价其作为高放废物处置库场地的适宜性,在过去的10 a,在该区开展了同位素水文地质调查工作.野外调查和氢、氧稳定同位素分析结果表明,研究区地下水主要源自大气降水补给.浅部地下水主要由现代区内降水补给形成,而深部地下水则可能由地质历史时期降水补给形成;浅部地下水系统具有相对开放性特征,水循环交替能力较强,而深部地下水系统具有相对封闭性特征,水循环交替能力较弱.     

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.     

Development of an apparatus to measure groundwater qualities in situ and to sample groundwater using boreholes

 To accurately measure the pH, Eh, EC and temperature of groundwater retrieved from boreholes, a deep groundwater sampling apparatus was developed which provided sensory measurements both in situ and in a flow-through cell at ground level. Under a pressure of 1×10⁶ Pa the in situ accuracy of the apparatus sensor was within the following limits: pH ±0.2, temperature ±0.1°C, Eh ±10 mV, and EC ±2.4%. The measuring and sampling of deep groundwater from a borehole of more than 1000 m in depth was performed continuously for 30 days. Values of pH were the same for the in situ sensor, the flow-through cell sensor and the laboratory measurements of the sampled water. At the beginning of the sampling period, Eh values of the in situ sensor indicated deep groundwater conditions. The apparatus is particularly useful for Eh measurement. Chemical composition and stable isotope ratios indicated that the groundwater sampled from more than 1000 m depth was a connate water with a chemical composition slightly different from seawater of the present time, and the groundwater retrieved from 800 m depth was a meteoric water. Natural radioactive elements are thought to be the origin of the tritium in the groundwater retrieved from the 1000 m depth. Received: 6 August 1996 / Accepted: 22 October 1996     

A Geochemical study of the groundwater in the Misli basin and environmental implications

The aim of this study was to determine geochemical properties of groundwater and thermal water in the Misli Basin and to assess thermal water intrusion into shallow groundwater due to over-extraction. According to isotope and hydrochemical analyses results, sampled waters can be divided into three groups: cold, thermal, and mixed waters. Only a few waters reach water–rock chemical equilibrium. Thermal waters in the area are characterized by Na⁺–Cl⁻–HCO₃⁻, while the cold waters by CaHCO₃ facies. On the basis of isotope results, thermal waters in the Misli basin are meteoric origin. In particular, δ¹⁸O and δ²H values of shallow groundwater vary from −10.2 to −12.2‰ and −71.2 to −82‰, while those of thermal waters range from −7.8 to −10.1‰ and from −67 to −74‰, respectively. The tritium values of shallow groundwater having short circulation as young waters coming from wells that range from 30 to 70 m in depth vary from 10 to 14 TU. The average tritium activity of groundwater in depths more than 100 m is 1.59 ± 1.16, which indicates long circulation. The rapid infiltration of the precipitation, the recycling of the evaporated irrigation water, the influence of thermal fluids and the heterogeneity of the aquifer make it difficult to determine groundwater quality changes in the Misli Basin. Obtained results show that further lowering of the groundwater table by over-consumption will cause further intrusion of thermal water which resulted in high mineral content into the fresh groundwater aquifer. Because of this phenomenon, the concentrations of some chemical components which impairs water quality in terms of irrigation purposes in shallow groundwaters, such as Na⁺, B, and Cl⁻, are highy probably expected to increase in time.     

Hydrochemical characteristics of groundwater in the Zhangye Basin, Northwestern China

The Zhangye Basin, located in arid northwest China, is an important agricultural and industrial center. In recent years rapid development has created an increased demand for water, which is increasingly being fulfilled by groundwater abstraction. Detailed knowledge of the geochemical evolution of groundwater and water quality can enhance understanding of the hydrochemical system, promoting sustainable development and effective management of groundwater resources. To this end, a hydrochemical investigation was conducted in the Zhangye Basin. Types of shallow groundwater in the Zhangye Basin were found to be HCO₃ ⁻, HCO₃ ⁻–SO₄ ²⁻, SO₄ ²⁻–HCO₃ ⁻, SO₄ ²⁻–Cl⁻, Cl⁻–SO₄ ²⁻ and Cl⁻ . The deep aquifer groundwater type was found to be HCO₃⁻–SO₄²⁻ throughout the entire area. Ionic ratio and saturation index calculations suggest that silicate rock weathering and evaporation deposition are the main processes that determine the ionic composition in the study area. The suitability of the groundwater for irrigation was assessed based on the US Salinity Laboratory salinity classification and the Wilcox diagram. In the study area, the compositions of the stable isotopes δ¹⁸O and δD in groundwater samples were found to range from −4.00 to −9.28‰ and from −34.0 to −65.0‰, respectively. These values indicate that precipitation is the main recharge source for the groundwater system; some local values indicate high levels of evaporation. Tritium analysis was used to estimate the ages of the different groundwaters; the tritium values of the groundwater samples varied from 3.13 to 36.62 TU. The age of the groundwater at depths of less than 30 m is about 5–10 years. The age of the groundwater at depths of 30–50 m is about 10–23 years. The age of the groundwater at depths of 50–100 m is about 12–29 years. For groundwater samples at depths of greater than 100 m, the renewal time is about 40 years.     

Hydrogeochemistry,groundwater ages and sources of salts in a granitic batholith on the Canadian Shield,southeastern Manitoba

The hydrogeochemistry of the Lac du Bonnet granitic batholith has been determined for the region of the Whiteshell Research Area (WRA) in southeastern Manitoba, Canada. This work forms part of the geosciences studies performed for the Canadian Nuclear Fuel Waste Management Program over the period 1980–1995 by Atomic Energy of Canada Limited (AECL). Knowledge of the variation of groundwater chemistry and its causes is useful in assessing the performance and safety of a nuclear fuel waste vault located at depths of up to 1000 m in a crystalline rock formation of the Canadian Shield. Groundwaters and matrix pore fluids have been obtained by standard sampling methods from shallow piezometers in clay-rich overburden, from packer-isolated borehole zones intersecting fractures or fault zones in the bedrock, and from boreholes in unfractured rock in AECL's Underground Research Laboratory (URL). Eighty-six individual fracture groundwaters have been sampled and analysed from permeable zones in 53 boreholes drilled to depths of up to 1000 m in the Lac du Bonnet batholith. In addition, 28 groundwaters from piezometers in a large wetland area near the URL have been sampled and analysed to determine the influence of clay-rich overburden on the bedrock hydrogeochemistry. Analyses have been made for major and minor ions, pH, Eh, trace metals, and stable and radioactive isotopes, to characterise these groundwaters and relate them to their hydrogeologic regimes. Shallow groundwaters in the fractured bedrock are generally dilute (TDS <0.3 g/l), Ca–Na–HCO₃ waters and show little indication of mixing with Ca–Mg–HCO₃–SO₄ groundwater from overburden sediments. The near-modern levels of ³H and ¹⁴C, and a warm-climate ²H/¹⁸O signature in these groundwaters, indicates that the upper ∼200 m of fractured bedrock contains an active groundwater circulation system with a residence time of tens to hundreds of years. Deeper fracture groundwaters (200–400 m depth) in recharge areas, are more alkaline, Na–Ca–HCO₃ waters and evolve to Na–Ca–HCO₃–Cl–SO₄ waters with increasing distance along the flow path. Isotopic data indicate the presence of a glacial melt-water component suggesting that the residence times of these waters are 10³–10⁵ a. These waters form a transition zone between the upper, advective flow regime and a deeper regime in sparsely fractured rock where groundwater in fractures and fracture zones is largely stagnant. At these depths (> 500 m), Na–Ca–Cl–SO₄ waters of increasing salinity (up to 50 g/l) with depth are found and in some fractures the waters have evolved to a Ca–Na–Cl composition. Isotopic data indicate that these waters are warm-climate and pre-glacial in origin, with residence times of over 1 Ma. Pore fluids observed to drain from the unfractured rock matrix in the URL facility are almost pure Ca–Cl in composition, ∼90 g/l salinity, and have a ²H/¹⁸O composition displaced well to the left of the global meteoric water line, about which all other WRA groundwaters lie. This information indicates that these pore fluids have undergone prolonged water-rock interaction and have residence times of 10¹–10³ Ma. Most of the deeper fracture groundwaters and pore fluids have low Br/Cl ratios and moderate to high δ³⁴S values of dissolved SO₄ which indicates that their salinity could be derived from a marine source such as the basinal sedimentary brines and evaporites to the west of the batholith. These fluids may have entered the batholith during early Paleozoic times when sedimentary rocks were deposited over the granite and were driven by a hydraulic gradient resulting from higher ground in western Canada. The hydrogeochemical data and interpretations show that below ∼500 m in the WRA, fracture-hosted groundwaters are very saline, reducing and old, and are, therefore, indicative of stagnant conditions over the period of concern for nuclear waste disposal (1 Ma). The intact rock matrix at these depths is extremely impermeable as indicated by the presence of pore fluids with unusual geochemical and isotopic characteristics. The pore fluids may represent basinal brines that have evolved geochemically and isotopically to their current composition over periods as long as 10³ Ma.     

A study of the interrelation between surface water and groundwater using isotopes and chlorofluorocarbons in Sanjiang plain,Northeast China

Surface water and groundwater are the main water resources used for drinking and production. Assessments of the relationship between surface water and groundwater provide information for water resource management in Sanjiang plain, Northeast China. The surface water (river, lake, and wetland) and groundwater were sampled and analyzed for stable isotopic (δD, δ ¹⁸O) composition, tritium, and chlorofluorocarbons concentrations. The local meteoric water line is δD = 7.3δ ¹⁸O–6.7. The tritium (T) and chlorofluorocarbon (CFC) contents in groundwater were analyzed to determine the groundwater ages. Most groundwater were modern water with the ages <50 years. The groundwaters in mountain area and near rivers were younger than in the central plain. The oxygen isotope (δ ¹⁸O) was used to quantify the relationship between surface water and groundwater. The Songhua, Heilongjiang, and Wusuli rivers were gaining rivers, but the shallow groundwater recharged from rivers at the confluence area of rivers. At the confluence of Songhua and Heilongjiang rivers, 88 % of the shallow groundwater recharged from Songhua river. The combination of stable isotopes, tritium, and CFCs was an effectively method to study the groundwater ages and interrelation between surface water and groundwater. Practically, the farmlands near the river and under foot of the mountain could be cultivated, but the farmlands in the central plain should be controlled.     

The Hydrogeochemistry Of Fractured Plutonic Rocks In The Canadian Shield

The composition of groundwater has been determined in selected granitic, gabbroic and gneissic plutons in the Canadian Shield as part of the Canadian Nuclear Fuel Waste Management Program. A similar geochemical evolution of the groundwater is seen with increasing depth or with flow along the hydraulic gradient, irrespective of rock type. This pattern is comparable to that seen in mine groundwaters from throughout the Canadian Shield. Near-surface groundwaters are typically dilute, slightly alkaline and Ca-(Na)-HCO₃ in composition. They evolve to higher pH, Na-(Ca)-HCO₃ compositions along the flow path because of interaction with plagioclase, calcite precipitation and ion exchange on clay minerals. At greater depths (>≈200 m), groundwater salinity increases as a result of the dissolution of Cl-rich salts in the rock matrix and, in certain areas, mixing with Na-Cl brines from seawater or basinal formation water. Stable and radioactive isotopic data for the groundwaters help to interpret these characteristics and indicate high residence times for the deeper, saline groundwater.

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3 évoluent du fait des interactions avec les plagioclases, de la précipitation de la calcite et des échanges d'ions avec les argiles. Aux plus grandes profondeurs (>≈200 m), l'accroissement de la salinité de l'eau souterraine est provoqué par la dissolution de chlorures de la matrice et, en certains endroits, par le mélange avec des saumures à Na et Cl d'eau de mer ou d'eau de formation de bassin. Les données des isotopes stables et radioactifs des eaux souterraines aident à interpréter leurs caractéristiques; elles indiquent des temps de séjour longs pour les eaux souterraines salées, les plus profondes.

     

Sampling and Characterizing Rare Earth Elements in Groundwater in Deep-Lying Fractures in Granitoids Under In Situ High-Pressure and Low-Redox Conditions

Several countries are preparing to dispose of radioactive nuclear waste deep underground in crystalline rock. This type of bedrock is commonly extensively fractured and consequently carries groundwater that serves as a medium for transporting metals and radionuclides. A group of metals of particular interest in this context is the rare earth elements (REEs), because they are analogues of actinides contained within radioactive waste and are tracers of hydrological pathways and geochemical processes. Concentrations of REEs are commonly low in these groundwaters, leading to values below detection limits of standard monitoring methods, particularly for the heavy REEs. We present a new technical set-up for monitoring REEs (and other trace metals) in groundwater in fractured crystalline rock. The technique consists of passing the fracture groundwater, commonly under high pressure and containing reduced chemical species, through a device that maintains the physicochemical character of the groundwater. Within the device, diffusive gradient in thin-film (DGT) discs are installed in triplicate. With this set-up, we studied REEs in groundwater in fractures at depths of approximately ?144, ?280, and ?450 m in granitoids in the Äspö Hard Rock Laboratory in southern Sweden. The entire REE suite was detected (concentrations down to 0.1 ng L^?1) and was differently fractionated among the groundwaters. The shallowest groundwater, composed of dilute modern Baltic Sea water, was enriched in the heavy REEs, whereas the deeper groundwaters, dominated by old saline water, were depleted in the heavy REEs. Deployment periods varying from 1 to 4 weeks delivered similar REE concentrations, indicating stability and reproducibility of the experimental set-up. The study finds that 1 week of deployment may be enough. However, if the overall setting and construction allow for longer deployment times, 2–3 weeks will be optimal in terms of reaching reliable REE concentrations well above the detection limit while maintaining the performance of the DGT samplers.     

The importance of unsaturated zone biogeochemical processes in determining groundwater composition, southeastern Australia

Analysis of soil, soil water and groundwater in the Mount William Creek catchment, southeastern Australia, shows that Mg²⁺ and Ca²⁺ within infiltrating rainfall are rapidly depleted by plant uptake and adsorption on clay minerals. Na⁺ and K⁺ may exhibit minor enrichment at shallow depths but are quickly readsorbed, so that cation/Cl^– ratios typical of groundwater are observed in soil water within the upper 200 cm of the soil profile for all species. The concentrations of K⁺ and Ca²⁺ in soil and groundwater are more depleted than Na⁺ and Mg²⁺ due to preferential uptake by vegetation. Removal of organic matter results in a continuing, long-term export of all major cations from the soil profiles. The processes of biogeochemical fractionation within the unsaturated zone rapidly modify the cation/Cl^– ratios of infiltrating rainfall to values characteristic of seawater. These mechanisms may have reached steady state, because groundwaters with seawater ion/Cl^– ratios are thousands of years old; the exchange sites on the soil clays are probably saturated, so cations supplied in rainfall are exported in organic matter and incorporated into recharge infiltrating into the groundwater. Much of the chemical evolution of groundwater traditionally attributed to processes within the aquifer is complete by the time recharge occurs; this evolutionary model may have broad application.     

Preliminary isotopic studies in the Bida basin,central Nigeria

The area of the Bida basin is lacking in essential data for effective groundwater management. Hydrological studies using environmental isotopes (²H,³H,¹³C,¹⁸O) were carried out in the basin during the 1987–1988 hydrological year on samples of rainfall, streams, springs, and groundwater. The results obtained results do not indicate the presence of paleowaters; rather all groundwaters in the basin are found to be of meteoric origin as bothD and ¹⁸O values of the samples, plotted in the conventional way, align with the meteoric water line (MWL). Moreover, these data show the deeper, and apparently older, groundwater to be more depleted in the heavy stable isotopes than the shallower, relatively younger groundwaters, indicating recharge under cooler climatic conditions for the former. Measured tritium values range from 0.7 to 23.8 TU and show a variation with both depth and lithology, while at the same time indicating that active recent recharge is taking place basin-wide. The few¹³C data available were used to illustrate the effect of pumping on the carbonate geochemistry of the groundwaters. Also, the stable isotope data from the basin were compared with similar data from other parts of the country to show the continental effect.     

Groundwater flow system under a rapidly urbanizing coastal city as determined by hydrogeochemistry

In the Jakarta area (Indonesia), excessive groundwater pumping due to the rapidly increasing population has caused groundwater-related problems such as brackish water contamination in coastal areas and land subsidence. In this study, we adopted multiple hydrogeochemical techniques to demonstrate the groundwater flow system in the Jakarta area. Although almost all groundwater existing in the Jakarta basin is recharged at similar elevations, the water quality and residence time demonstrates a clear difference between the shallow and deep aquifers. Due to the rapid decrease in the groundwater potential in urban areas, we found that the seawater intrusion and the shallow and deep groundwaters are mixing, a conclusion confirmed by major ions, Br^?:Cl^? ratios, and chlorofluorocarbon (CFC)-12 analysis. Spring water and groundwater samples collected from the southern mountainside area show younger age characteristics with high concentrations of ¹⁴C and Ca–HCO₃ type water chemistry. We estimated the residence times of these groundwaters within 45 years under piston flow conditions by tritium analysis. Also, these groundwater ages can be limited to 20–30 years with piston flow evaluated by CFCs. Moreover, due to the magnitude of the CFC-12 concentration, we can use a pseudo age indicator in this field study, because we found a positive correlation between the major type of water chemistry and the CFC-12 concentration.     

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.     

An assessment of the origin and variation of groundwater salinity in southeastern Ghana

Groundwater from the major aquifers in southeastern part of Ghana was sampled to determine the main controls on groundwater salinity in the area. This paper uses multivariate statistical methods, conventional graphical methods and stable isotope data to determine spatial relationships among groundwaters from the different hydrogeologic units in the area on the basis of salinity. Q-mode hierarchical cluster analysis (HCA) was used to spatially classify the samples, whilst R-mode factor analysis was used to reduce the dataset into two major principal components representing the sources of variation in the hydrochemistry. Analysis of the major chemical parameters suggests that the principal component responsible for salinity increment in the area is the weathering of minerals in the aquifers. This factor is especially more significant in the upland areas away from the coast. The second factor responsible for salinity in the area is the combined effects of seawater intrusion, and anthropogenic activities. This study finds that four major spatial groundwater groups exist in the area: low salinity, acidic groundwaters which are mainly derived from the Birimian and Togo Series aquifers; low salinity, moderate to neutral pH groundwaters which are mainly from the Voltaian, Buem and Cape Coast granitoids; very high salinity waters which are not suitable for most domestic and irrigation purposes and are mainly from the Keta aquifers; and intermediate salinity groundwaters comprising groundwater from the Keta basin aquifers with minor contributions from the other major terrains. The major water type identified in this study is the Ca–Mg–HCO₃ type, which degrades into predominantly Na–Cl–SO₄ more saline groundwaters toward the coast. Stable isotope data analyses suggest that groundwater in the Voltaian aquifers is largely of recent meteoric origin. The Birimian and Togo aquifers receive a component of recharge from the tributaries of the Densu and Volta Rivers, after the waters have undergone evaporative enrichment of the heavier isotopes. In the Keta basin, recharge is mainly from precipitation but an observed enrichment of ²H and ¹⁸O isotopes is probably due to seawater and evaporative effects since the water table there is very shallow. An analysis of the irrigation quality of groundwater from the six aquifers in the study area using sodium adsorption ratio and electrical conductivity suggests that most of the aquifers supply groundwater of acceptable quality for irrigation. The only exception is the Keta Basin area, where extremely high salinities and SAR values render groundwater from this basin unsuitable for irrigation purposes.     

Groundwater recharge estimation using chloride,stable isotopes and tritium profiles in the sands of northwestern Senegal

A study of environmental chloride, deuterium, oxygen-18, and tritium in deep sand profiles (35 m) has been carried out in order to estimate their relative value for measuring average groundwater recharge. The investigation was located at a 0.1-km² site in Quaternary sands near the northwestern coast of Senegal in a zone of rainfed agriculture. By using a steady-state model for duplicate unsaturated zone chloride profiles, the long-term average recharge at the site was estimated to be 30 mm yr^–1 or around 10% of the average precipitation (290 mm). The chloride concentration of adjacent shallow groundwater was relatively uniform and comparable to the unsaturated zone average, while the spatial variability in the depth distribution of Cl^– in the unsaturated zone was considerable. Stable isotope (deuterium and oxygen-18) data show that there is some isotopic enrichment due to direct evaporation through the soil surface. The degree of heavy isotope enrichment is proportional to the extent of evaporative loss and there is good correspondance with the chloride enrichment. Nevertheless, stable isotopes cannot be used quantitatively to estimate the recharge. The excellent preservation of the peak in thermonuclear tritium in precipitation in the unsaturated zone at depths between 12 and 20 m enables an estimated annual recharge of 24 mm yr^–1 in this area to be calculated, using the piston flow model. Agreement therefore between Cl and³H as tools for recharge measurement is reasonable over the site.     

Hydrological and reactive processes during rapid recharge to fracture zones: The Äspö large scale redox experiment

The hydrochemical response of fracture zones to enhanced recharge into the upper bedrock environment has been studied during a 3 a project at the Äspö Hard Rock Laboratory (HRL) in Southeastern Sweden. Hydrochemical data obtained during the experiment provides a basis for development of a model for the impact of accelerated recharge on groundwater composition and reactive processes during repository construction and operation. Tunnel construction at the HRL resulted in a 50-fold increase in recharge rates, and a 30-fold decrease in groundwater residence times in the fracture zone studied. Up to 80% dilution of the native groundwater created the greatest impact on groundwater composition. In addition, comparison of mass balances for solutes with known conservative behaviour, and reactive solutes, indicates a significant source of HCO⁻₃, SO²⁻₄ and Na⁺ ions and a significant sink for Ca²⁺ ions within the fracture zone. These trends are explained by ion-exchange processes and microbial degradation of organic C transported from the soil with recharge. The increased microbial activity helps maintain anoxic conditions within the fracture zone. The enhanced recharge favours the performance of the geological barrier since anoxic conditions help to protect against corrosion of engineered barriers, and because long-lived isotopes of Np, Tc and U are less soluble under reducing conditions. A secondary impact is the strong dilution which affects trace element speciation, and also the stability and possible transport of colloids, through ion strength effects. Results from this experiment are primarily significant for national radioactive waste disposal programs that consider potential repository sites in granite geology, and for other programs considering disposal in fractured rock.     

Environmental isotopic and hydrochemical study of water in the karst aquifer and submarine springs of the Syrian coast

The groundwater of major karst systems and submarine springs in the coastal limestone aquifer of Syria has been investigated using chemical and isotopic techniques. The δ¹⁸O values of groundwater range from ?6.8 to ?5.05‰, while those for submarine springs vary from ?6.34 to +1.08‰ (eastern Mediterranean seawater samples have a mean of +1.7‰). Groundwater originates from the direct infiltration of atmospheric water. Stable isotopes show that the elevation of the recharge zones feeding the Banyas area (400–600 m a.s.l.) is higher than that feeding the Amrit area (100–300 m a.s.l.). The ¹⁸O_extracted (¹⁸O content of the seawater contribution) for the major submarine springs suggests a mean recharge area elevation of 600–700 m a.s.l., and lower than 400 m a.s.l. for the spring close to Amrit. Based on the measured velocity and the percentage of fresh water at the submarine springs outlet, the estimated discharge rate is 350 million m³/year. The tritium concentrations in groundwater (1.6–5.9 TU) are low and very close to the current rainfall values (2.9–5.6 TU). Adopting a model with exponential time distribution, the mean turnover time of groundwater in the Al-sen spring was evaluated to be 60 years. A value of about 3.7 billion m³ was obtained for the maximum groundwater reservoir size.     

Groundwater quality in a coastal area: a case study from Andhra Pradesh, India

Over-exploitation of groundwater results in decline of water levels, leading to intrusion of salt water along the coastal region, which is a natural phenomenon. A groundwater quality survey has been carried out to assess such phenomena along the coast of Visakhapatnam, Andhra Pradesh, India. Brackish groundwaters are observed in most of the wells. The rest of the wells show a fresh water environment. The factors responsible for the brackish groundwater quality with respect to the influence of seawater are assessed, using the standard ionic ratios, such as Ca²⁺:Mg²⁺, TA:TH and Cl⁻:HCO⁻ ₃. Results suggest that the brackish nature in most of the groundwaters is not due to the seawater influence, but is caused by the hydrogeochemical process. Some influence of seawater on the groundwater quality is observed along the rock fractures. The combined effect of seawater and urban wastewaters is due to the inferior quality of groundwater in a few wells, where they are at topographic lows close to the coast.     

Comparison of the Sr isotopic signatures in brines of the Canadian and Fennoscandian shields

A synthesis of Sr isotope data from shallow and deep groundwaters, and brines from the Fennoscandian and Canadian Shields is presented. A salinity gradient is evident in the water with concentrations varying from approximately 1–75 g L⁻¹ below 1500 m depth in the Fennoscandian Shield and from 10 up to 300 g L⁻¹ below 650 m depth in the Canadian Shield. Strontium isotope ratios were measured to assess the origin of the salinity and evaluate the degree of water–rock interaction in the systems. In both shields, the Sr concentrations are enriched relative to Cl, defining a positive trend parallel to the seawater dilution line and indicative of Sr addition through weathering processes. The depth distribution for Sr concentration increases strongly with increasing depth in both shields although the variation in Sr-isotope composition does not mirror that of Sr concentrations. Strontium-isotope compositions are presented for surface waters, and groundwaters in several sites in the Fennoscandian and Canadian Shields. Numerous mixing lines can be drawn reflecting water–rock interaction. A series of calculated lines links the surface end-members (surface water and shallow groundwater) and the deep brines; these mixing lines define a range of ⁸⁷Sr/⁸⁶Sr ratios for the deep brines in different selected sites. All sites show a specific ⁸⁷Sr/⁸⁶Sr signature and the occurrence of large ⁸⁷Sr/⁸⁶Sr variations is site specific in both shields. In Canadian Shield brines, the Sr isotope ratios clearly highlight large water rock interaction that increases the ⁸⁷Sr/⁸⁶Sr ratio from water that could have been of marine origin. In contrast to the Canadian Shield, groundwater does not occur in closed pockets in the Fennoscandian, and the well-constrained ⁸⁷Sr/⁸⁶Sr signatures in deep brines should correspond to a large, well-mixed and homogeneous water reservoir, whose Sr isotope signature results from water–rock interaction.