Hydrochemical characterization of complex volcanic aquifers in a continental rifted zone: the Middle Awash basin, Ethiopia

The Middle Awash basin is an arid region in Ethiopia where surface waters are scarce and local communities are dependent on groundwater resources for water supply. The complex hydrogeological system of this basin has been conceptualized. Multivariate statistical analysis of hydrochemical variables and water isotopes were used to study the rock?Cwater interaction, geochemical reaction processes and the hydrological link between aquifers. Groundwaters from aquifers of the high-rainfall plateau bounding the rift are slightly mineralized, as well as depleted in ??¹⁸O and ??D, and contain ³H above 0.8?TU. This suggests a low degree of rock?Cwater interaction and that groundwater is under recharge from heavy rain that falls on surrounding highlands. On the other hand, groundwaters from aquifers of the rift floor are highly mineralized and show slight enrichment in ??¹⁸O and ??D with positive oxygen shift, but contain ³H below 0.8?TU. The positive oxygen shift in rift floor groundwaters may be caused by the isotopic exchange of oxygen between groundwater and aquifer materials during rock?Cwater interaction, whereas the low ³H content could be due to the decay of tritium along relatively long flow paths. The approach utilized in this study may be applicable to understanding hydrogeochemical processes in other complex volcanic terrains.     

Groundwaters of the Central Ethiopian Rift: diagnostic trends in trace elements, δ<Superscript>18</Superscript>O and major elements

The Ethiopian Rift (a major portion of the Great East African Rift) is characterized by a narrow elongated depression bounded by highlands from both sides. This topographic configuration leads to a monsoon redistribution which resulted in an arid rift floor and humid high rainfall highlands. The rifting and associated volcanism also caused a thinning of the crust and facilitates influx of CO₂ and other mantle gases as diffuse sources or along faults from deeper sources. Groundwaters in the rift floor are usually of high mineral content (high F, U, As and salinity) while those on the plateau are of low mineral content. Among many factors, groundwater availability and quality in the rift floor aquifers is the function of their connection to the aquifers in the high rainfall plateau and the residence time of groundwater prior to reaching the rift floor. This entails the need for addressing one basic hydrologic question in such a setting: at what depth and rate does recharge from the high rainfall highland reach the lowland rift aquifers? This study uses spatial variations in trace elements and relates them to ¹⁴C variations, thereby investigating the suitability of using trace elements as proxies for residence time estimation of groundwaters of relatively short (1,000–2,000 years) residence time. This work also investigates the behavior of trace element trends along the groundwater flow path in a rifted setting and compares them with such trends in sedimentary aquifers elsewhere. The comparison shows a clear difference in behavior of trace elements along the groundwater flow path when compared with such variations in big sedimentary basins with no prominent rifting and volcanism, suggesting the need of calibrating the relation between trace elements and any direct residence time indicators. An integrated use of major elements, trace elements, and environmental isotopes reveals that the main recharge of the aquifers originates from mountain blocks and that recharge takes place via fractures with no evidence of evaporation prior to recharge. Redox processes appear to play a limited role in trace element geochemistry of groundwaters in the region. Progressive trends in trace element composition along the groundwater flow path suggest continuous groundwater flow from the plateau.     

The distribution and hydrogeological controls of fluoride in the groundwater of central Ethiopian rift and adjacent highlands

Occurrence of fluoride (F) in groundwater has drawn worldwide attention, since it has considerable impact on human health. In Ethiopia high concentrations of F in groundwaters used for community water supply have resulted in extensive dental and skeletal fluorosis. As a part of a broader study, the distribution of F in groundwater has been investigated, and compared with bedrock geology and pertinent hydrochemical variables. The result indicates extreme spatial variations. High F concentration is often associated with active and sub-active regional thermal fields and acidic volcanics within high temperature rift floor. Variations in F can also be related to changes in calcium concentration resulting from dissolution of calcium minerals and mixing with waters of different chemical composition originated from variable hydrogeological environment across the rift valley. The concentration of F dramatically declines from the rift towards the highlands with the exception of scattered points associated with thermal springs confined in local volcanic centers. There are also interactions of F-rich alkaline lakes and the surrounding groundwater. Meteoric waters recharging volcanic aquifers become enriched with respect to F along the groundwater flow path from highland recharge areas to rift discharge areas. Locally wells drilled along large rift faults acting as conduits of fresh highland waters show relatively lower F. These areas are likely to be possible sources of better quality waters within the rift. The result of this study has important implications on site selection for water well drilling.     

Paleowaters in Silurian-Devonian carbonate aquifers: Geochemical evolution of groundwater in the Great Lakes region since the Late Pleistocene

Changes in the climatic conditions during the Late Quaternary and Holocene greatly impacted the hydrology and geochemical evolution of groundwaters in the Great Lakes region. Increased hydraulic gradients from melting of kilometer-thick Pleistocene ice sheets reorganized regional-scale groundwater flow in Paleozoic aquifers in underlying intracratonic basins. Here, we present new elemental and isotopic analyses of 134 groundwaters from Silurian-Devonian carbonate and overlying glacial drift aquifers, along the margins of the Illinois and Michigan basins, to evaluate the paleohydrology, age distribution, and geochemical evolution of confined aquifer systems. This study significantly extends the spatial coverage of previously published groundwaters in carbonate and drift aquifers across the Midcontinent region, and extends into deeper portions of the Illinois and Michigan basins, focused on the freshwater-saline water mixing zones. In addition, the hydrogeochemical data from Silurian-Devonian aquifers were integrated with deeper basinal fluids, and brines in Upper Devonian black shales and underlying Cambrian-Ordovician aquifers to reveal a regionally extensive recharge system of Pleistocene-age waters in glaciated sedimentary basins. Elemental and isotope geochemistry of confined groundwaters in Silurian-Devonian carbonate and glacial drift aquifers show that they have been extensively altered by incongruent dissolution of carbonate minerals, dissolution of halite and anhydrite, cation exchange, microbial processes, and mixing with basinal brines. Carbon isotope values of dissolved inorganic carbon (DIC) range from −10 to −2‰, ⁸⁷Sr/⁸⁶Sr ratios range from 0.7080 to 0.7090, and δ³⁴S-SO₄ values range from +10 to 30‰. A few waters have elevated δ¹³C_DIC values (>15‰) from microbial methanogenesis in adjacent organic-rich Upper Devonian shales. Radiocarbon ages and δ¹⁸O and δD values of confined groundwaters indicate they originated as subglacial recharge beneath the Laurentide Ice Sheet (14-50 ka BP, −15 to −13‰ δ¹⁸O). These paleowaters are isolated from shallow flow systems in overlying glacial drift aquifers by lake-bed clays and/or shales. The presence of isotopically depleted waters in Paleozoic aquifers at relatively shallow depths illustrates the importance of continental glaciation on regional-scale groundwater flow. Modern groundwater flow in the Great Lakes region is primarily restricted to shallow unconfined glacial drift aquifers. Recharge waters in Silurian-Devonian and unconfined drift aquifers have δ¹⁸O values within the range of Holocene precipitation: −11 to −8‰ and −7 to −4.5‰ for northern Michigan and northern Indiana/Ohio, respectively. Carbon and Sr isotope systematics indicate shallow groundwaters evolved through congruent dissolution of carbonate minerals under open and closed system conditions (δ¹³C_DIC = −14.7 to−11.1‰ and ⁸⁷Sr/⁸⁶Sr = 0.7080-0.7103). The distinct elemental and isotope geochemistry of Pleistocene- versus Holocene-age waters further confirms that surficial flow systems are out of contact with the deeper basinal-scale flow systems. These results provide improved understanding of the effects of past climate change on groundwater flow and geochemical processes, which are important for determining the sustainability of present-day water resources and stability of saline fluids in sedimentary basins.     

Dissolved noble gases and stable isotopes as tracers of preferential fluid flow along faults in the Lower Rhine Embayment,Germany

Groundwater in shallow unconsolidated sedimentary aquifers close to the Bornheim fault in the Lower Rhine Embayment (LRE), Germany, has relatively low δ²H and δ¹⁸O values in comparison to regional modern groundwater recharge, and ⁴He concentrations up to 1.7?×?10^?4 cm³ (STP) g^–1?±?2.2 % which is approximately four orders of magnitude higher than expected due to solubility equilibrium with the atmosphere. Groundwater age dating based on estimated in situ production and terrigenic flux of helium provides a groundwater residence time of ～10⁷ years. Although fluid exchange between the deep basal aquifer system and the upper aquifer layers is generally impeded by confining clay layers and lignite, this study’s geochemical data suggest, for the first time, that deep circulating fluids penetrate shallow aquifers in the locality of fault zones, implying  that sub-vertical fluid flow occurs along faults in the LRE. However, large hydraulic-head gradients observed across many faults suggest that they act as barriers to lateral groundwater flow. Therefore, the geochemical data reported here also substantiate a conduit-barrier model of fault-zone hydrogeology in unconsolidated sedimentary deposits, as well as corroborating the concept that faults in unconsolidated aquifer systems can act as loci for hydraulic connectivity between deep and shallow aquifers. The implications of fluid flow along faults in sedimentary basins worldwide are far reaching and of particular concern for carbon capture and storage (CCS) programmes, impacts of deep shale gas recovery for shallow groundwater aquifers, and nuclear waste storage sites where fault zones could act as potential leakage pathways for hazardous fluids.     

黑河下游额济纳盆地深层地下水来源的探讨

本文作者在额济纳盆地进行了长达3年的研究,获得了大量盆地地下水资料和水化学、同位素分析数据,在此基础上,利用水化学和环境同位素示踪技术,结合盆地水文地质条件,对盆地深层地下水的补给来源和循环特征进行了探讨.水化学和同位素结果显示,黑河流域深层地下水补给来源具有多源性,主要为核爆前形成的“老水”,水循环缓慢.在进行流域水资源开发时,对深层地下水的利用一定要慎重.     

Characterisation of recharge processes and groundwater flow mechanisms in weathered-fractured granites of Hyderabad (India) using isotopes

In order to address the problem of realistic assessment of groundwater potential and its sustainability, it is vital to study the recharge processes and mechanism of groundwater flow in fractured hard rocks, where inhomogeneties and discontinuities have a dominant role to play. Wide variations in chloride, δ¹⁸O and ¹⁴C concentrations of the studied groundwaters observed in space and time could only reflect the heterogeneous hydrogeological setting in the fractured granites of Hyderabad (India). This paper, based on the observed isotopic and environmental chloride variations of the groundwater system, puts forth two broad types of groundwaters involving various recharge processes and flow mechanisms in the studied granitic hard rock aquifers. Relatively high ¹⁴C ages (1300 to ～6000 yr B.P.), δ¹⁸O content (?3.2 to ?1.5‰) and chloride concentration (<100 mg/l) are the signatures that identified one broad set of groundwaters resulting from recharge through weathered zone and subsequent movement through extensive sheet joints. The second set of groundwaters possessed an age range Modern to ～1000 yr B.P., chloride in the range 100 to ～350 mg/l and δ¹⁸O from ?3.2 to +1.7‰. The δ¹⁸O enrichment and chloride concentration, further helped in the segregation of the second set of groundwaters into three sub-sets characterized by different recharge processes and sources. Based on these processes and mechanisms, a conceptual hydrogeologic model has evolved suggesting that the fracture network is connected either to a distant recharge source or to a surface reservoir (evaporating water bodies) apart from overlying weathered zone, explaining various resultant groundwaters having varying ¹⁴C ages, chloride and δ¹⁸O concentrations. The surface reservoir contribution to groundwater is evaluated to be significant (40 to 70%) in one subset of groundwaters. The conceptual hydrogeologic model, thus evolved, can aid in understanding the mechanism of groundwater flow as well as migration of contaminants to deep groundwater in other fractured granitic areas.     

Groundwater flow dynamics in the complex aquifer system of Gidabo River Basin (Ethiopian Rift): a multi-proxy approach

Hydrochemical and isotope data in conjunction with hydraulic head and spring discharge observations were used to characterize the regional groundwater flow dynamics and the role of the tectonic setting in the Gidabo River Basin, Ethiopian Rift. Both groundwater levels and hydrochemical and isotopic data indicate groundwater flow from the major recharge area in the highland and escarpment into deep rift floor aquifers, suggesting a deep regional flow system can be distinguished from the shallow local aquifers. The δ¹⁸O and δ²H values of deep thermal (≥30 °C) groundwater are depleted relative to the shallow (<60 m below ground level) groundwater in the rift floor. Based on the δ¹⁸O values, the thermal groundwater is found to be recharged in the highland around 2,600 m a.s.l. and on average mixed with a proportion of 30 % shallow groundwater. While most groundwater samples display diluted solutions, δ¹³C data of dissolved inorganic carbon reveal that locally the thermal groundwater near fault zones is loaded with mantle CO₂, which enhances silicate weathering and leads to anomalously high total dissolved solids (2,000–2,320 mg/l) and fluoride concentrations (6–15 mg/l) exceeding the recommended guideline value. The faults are generally found to act as complex conduit leaky barrier systems favoring vertical mixing processes. Normal faults dipping to the west appear to facilitate movement of groundwater into deeper aquifers and towards the rift floor, whereas those dipping to the east tend to act as leaky barriers perpendicular to the fault but enable preferential flow parallel to the fault plane.     

Groundwater recharge,circulation and geochemical evolution in the source region of the Blue Nile River,Ethiopia

Geochemical and environmental isotope data were used to gain the first regional picture of groundwater recharge, circulation and its hydrochemical evolution in the upper Blue Nile River basin of Ethiopia. Q-mode statistical cluster analysis (HCA) was used to classify water into objective groups and to conduct inverse geochemical modeling among the groups. Two major structurally deformed regions with distinct groundwater circulation and evolution history were identified. These are the Lake Tana Graben (LTG) and the Yerer Tullu Wellel Volcanic Lineament Zone (YTVL). Silicate hydrolysis accompanied by CO₂ influx from deeper sources plays a major role in groundwater chemical evolution of the high TDS Na–HCO₃ type thermal groundwaters of these two regions. In the basaltic plateau outside these two zones, groundwater recharge takes place rapidly through fractured basalts, groundwater flow paths are short and they are characterized by low TDS and are Ca–Mg–HCO₃ type waters. Despite the high altitude (mean altitude ∼2500 masl) and the relatively low mean annual air temperature (18 °C) of the region compared to Sahelian Africa, there is no commensurate depletion in δ¹⁸O compositions of groundwaters of the Ethiopian Plateau. Generally the highland areas north and east of the basin are characterized by relatively depleted δ¹⁸O groundwaters. Altitudinal depletion of δ¹⁸O is 0.1‰/100 m. The meteoric waters of the Blue Nile River basin have higher d-excess compared to the meteoric waters of the Ethiopian Rift and that of its White Nile sister basin which emerges from the equatorial lakes region. The geochemically evolved groundwaters of the YTVL and LTG are relatively isotopically depleted when compared to the present day meteoric waters reflecting recharge under colder climate and their high altitude.     

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.     

Geochemical indicators of interbasin groundwater flow within the southern Rio Grande Valley, southwestern USA

Increased groundwater withdrawals for the growing population in the Rio Grande Valley and likely alteration of recharge to local aquifers with climate change necessitates an understanding of the groundwater connection between the Jornada del Muerto Basin and the adjoining and more heavily used aquifer in the Mesilla Basin. Separating the Jornada and Mesilla aquifers is a buried bedrock high from Tertiary intrusions. This bedrock high or divide restricts and/or retards interbasin flow from the Jornada aquifer into the Mesilla aquifer. The potentiometric surface of the southern Jornada aquifer near part of the bedrock high indicates a flow direction away from the divide because of a previously identified damming effect, but a groundwater outlet from the southern Jornada aquifer is necessary to balance inputs from the overall Jornada aquifer. Differences in geochemical constituents (major ions, δD, δ¹⁸O, δ³⁴S, and ⁸⁷Sr/⁸⁶Sr) indicate a deeper connection between the two aquifers through the Tertiary intrusions where Jornada water is geochemically altered because of a geothermal influence. Jornada groundwater likely is migrating through the bedrock high in deeper pathways formed by faults of the Jornada Fault Zone, in addition to Jornada water that overtops the bedrock high as previously identified as the only connection between the two aquifers. Increased groundwater withdrawals and lowering of the potentiometric surface of the Jornada aquifer may alter this contribution ratio with less overtopping of the bedrock high and a continued deeper flowpath contribution that could potentially increase salinity values in the Mesilla Basin near the divide.     

Regional groundwater flow and geochemical evolution in the Amacuzac River Basin,Mexico

An approach is presented to investigate the regional evolution of groundwater in the basin of the Amacuzac River in Central Mexico. The approach is based on groundwater flow cross-sectional modeling in combination with major ion chemistry and geochemical modeling, complemented with principal component and cluster analyses. The hydrogeologic units composing the basin, which combine aquifers and aquitards both in granular, fractured and karstic rocks, were represented in sections parallel to the regional groundwater flow. Steady-state cross-section numerical simulations aided in the conceptualization of the groundwater flow system through the basin and permitted estimation of bulk hydraulic conductivity values, recharge rates and residence times. Forty-five water locations (springs, groundwater wells and rivers) were sampled throughout the basin for chemical analysis of major ions. The modeled gravity-driven groundwater flow system satisfactorily reproduced field observations, whereas the main geochemical processes of groundwater in the basin are associated to the order and reactions in which the igneous and sedimentary rocks are encountered along the groundwater flow. Recharge water in the volcanic and volcano-sedimentary aquifers increases the concentration of HCO₃ ^–, Mg²⁺ and Ca²⁺ from dissolution of plagioclase and olivine. Deeper groundwater flow encounters carbonate rocks, under closed CO₂ conditions, and dissolves calcite and dolomite. When groundwater encounters gypsum lenses in the shallow Balsas Group or the deeper Huitzuco anhydrite, gypsum dissolution produces proportional increased concentration of Ca²⁺ and SO₄ ^2–; two samples reflected the influence of hydrothermal fluids and probably halite dissolution. These geochemical trends are consistent with the principal component and cluster analyses.     

Defining the dynamics of groundwater in Serra da Estrela Mountain area, central Portugal: an isotopic and hydrogeochemical approach

In a multidisciplinary approach, geological, geomorphologic, structural, hydrogeochemical and isotopic surveys were conducted on the Serra da Estrela groundwater system (central Portugal) in order to establish/develop a conceptual circulation model of the Caldas de Manteigas thermomineral system. A detailed study of the isotopic and geochemical composition of surface waters (e.g. Zêzere River), shallow groundwaters (cold dilute springs), and thermomineral waters was carried out to characterize the distribution of isotopes in waters of this mountainous region, and to determine the origin and possible recharge locations of the thermomineral system. Special attention was dedicated to isotopic tracers and their role in the definition of the thermomineral waters??conceptual model, considering: (1) the δ¹⁸O fractionation gradient; (2) the mean isotopic composition of the thermomineral waters in the region; and (3) the estimation of snowmelt contribution as a source of groundwater recharge at Serra da Estrela. The recharge of the thermomineral aquifer takes place on the more permeable zones of the granitic massif, associated with the main tectonic structures, whereas the recharge of the shallow aquifers seems to take place mostly in the plateaus, although another part of the recharge may occur in the slopes of the Zêzere River valley.     

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.     

Residence times of shallow groundwater in West Africa: implications for hydrogeology and resilience to future changes in climate

Although shallow groundwater (<50 mbgl) sustains the vast majority of improved drinking-water supplies in rural Africa, there is little information on how resilient this resource may be to future changes in climate. This study presents results of a groundwater survey using stable isotopes, CFCs, SF₆, and ³H across different climatic zones (annual rainfall 400–2,000 mm/year) in West Africa. The purpose was to quantify the residence times of shallow groundwaters in sedimentary and basement aquifers, and investigate the relationship between groundwater resources and climate. Stable-isotope results indicate that most shallow groundwaters are recharged rapidly following rainfall, showing little evidence of evaporation prior to recharge. Chloride mass-balance results indicate that within the arid areas (<400 mm annual rainfall) there is recharge of up to 20 mm/year. Age tracers show that most groundwaters have mean residence times (MRTs) of 32–65 years, with comparable MRTs in the different climate zones. Similar MRTs measured in both the sedimentary and basement aquifers suggest similar hydraulic diffusivity and significant groundwater storage within the shallow basement. This suggests there is considerable resilience to short-term inter-annual variation in rainfall and recharge, and rural groundwater resources are likely to sustain diffuse, low volume abstraction.     

Investigation by multivariate analysis of groundwater composition in a multilayer aquifer system from North Africa: A multi-tracer approach

A multi-tracer approach has been carried out in the Sbeïtla multilayer aquifer system, central Tunisia, to investigate the geochemical evolution, the origin of groundwaters and their circulation patterns. It involves statistical data analysis coupled with the definition of the hydrochemical and isotopic features of the different groundwaters. Principal Components Analysis (PCA) of geochemical data used in conjunction with bivariate diagrams of major and trace elements indicate that groundwater mineralization is mainly controlled by water-rock interaction and anthropogenic processes in relation to return flow of irrigation waters. The PCA of isotopic data and bivariate conventional diagrams of stable and radiogenic isotopes i.e. δ¹⁸O vs. δ²H and δ¹⁸O vs. ¹⁴C provide valuable information about the origin and the circulation patterns of the different groundwater groups. They permit classifying groundwaters into three groups. The first group is characterized by low ³H concentrations, low ¹⁴C activities and depleted stable isotope contents. It corresponds to an old end-member in relation with palaeoclimatic recharge which occurred during the Late Pleistocene and the Early Holocene humid periods. The second group is distinguished by high to moderate ³H concentrations, high ¹⁴C activities and enriched heavy isotope signatures. It corresponds to a modern end-member originating from a mixture of post-nuclear and present-day recharge in relation to return flow of irrigation waters. The third group is characterized by an average composition of stable and radiogenic isotope signatures. It provides evidence for the mixing between the upward moving palaeoclimatic end-member and the downward moving present-day end-member.     

Delineating volcanic aquifer recharge areas using geochemical and isotopic tools

Relative recharge areas are evaluated using geochemical and isotopic tools, and inverse modeling. Geochemistry and water quality in springs discharging from a volcanic aquifer system in Guatemala are related to relative recharge area elevations and land use. Plagioclase feldspar and olivine react with volcanically derived CO₂ to produce Ca-montmorillonite, chalcedony and goethite in the groundwater. Alkalinity, Mg, Ca, Na, and SiO_2(aq) are produced, along with minor increases in Cl and SO₄ concentrations. Variations in groundwater δD and δ¹⁸O values are attributed to recharge elevation and used in concert with geochemical evolution to distinguish local, intermediate, and regional flow systems. Springs with geochemically inferred short flow paths provided useful proxies to estimate an isotopic gradient for precipitation (??.67 δ¹⁸O/100?m). No correlation between spring discharge and relative flow-path length or interpreted recharge elevation was observed. The conceptual model was consistent with evidence of anthropogenic impacts (sewage and manure) in springs recharged in the lower watershed where livestock and humans reside. Spring sampling is a low-budget approach that can be used to develop a useful conceptual model of the relative scale of groundwater flow (and appropriate watershed protection areas), particularly in volcanic terrain where wells and boreholes are scarce.     

Hydrogeochemical genesis of groundwaters with abnormal fluoride concentrations from Zhongxiang City,Hubei Province,central China

The groundwaters from Zhongxiang City, Hubei Province of central China, have high fluoride concentration up to 3.67 mg/L, and cases of dental fluorosis have been found in this region. To delineate the nature and extent of high fluoride groundwaters and to assess the major geochemical factors controlling the fluoride enrichment in groundwater, 14 groundwater samples and 5 Quaternary sediment samples were collected and their chemistry were determined in this study. Some water samples from fissured hard rock aquifers and Quaternary aquifers have high fluoride concentrations, whereas all karst water samples contain fluoride less than 1.5 mg/L due to their high Ca/Na ratios. For the high fluoride groundwaters in the fissured hard rocks, high HCO₃ ⁻ concentration and alkaline condition favor dissolution of fluorite and anion exchange between OH⁻ in groundwater and exchangeable F⁻ in some fluoride-bearing minerals. For fluoride enrichment in groundwaters of Quaternary aquifers, high contents of fluoride in the aquifer sediments and evapotranspiration are important controls.     

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.     

Evaluation of groundwater dynamics and quality in the Najd aquifers located in the Sultanate of Oman

The Najd, Oman, is located in one of the most arid environments in the world. The groundwater in this region is occurring in four different aquifers A to D of the Hadhramaut Group consisting mainly of different types of limestone and dolomite. The quality of the groundwater is dominated by the major ions sodium, calcium, magnesium, sulphate, and chloride, but the hydrochemical character is varying among the four aquifers. Mineralization within the separate aquifers increases along the groundwater flow direction from south to north-northeast up to high saline sodium-chloride water in aquifer D in the northeast area of the Najd. Environmental isotope analyses of hydrogen and oxygen were conducted to monitor the groundwater dynamics and to evaluate the recharge conditions of groundwater into the Najd aquifers. Results suggest an earlier recharge into these aquifers as well as ongoing recharge takes place in the region down to present day. Mixing of modern and submodern waters was detected by water isotopes in aquifer D in the mountain chain (Jabal) area and along the northern side of the mountain range. In addition, δ²H and δ¹⁸O variations suggest that aquifers A, B, and C are assumed to be connected by faults and fractures, and interaction between the aquifers may occur. Low tritium concentrations support the mixing assumption in the recharge area. The knowledge about the groundwater development is an important factor for the sustainable use of water resources in the Dhofar region.