Groundwater origin and flow along selected transects in Ethiopian rift volcanic aquifers

The disruption of lithologies by cross-cutting faults and the variability in volcanic structures make the hydrogeology of the rifted volcanic terrain in Ethiopia very complex. Along two transects, selected due to their hydrogeologic characteristics, groundwater flow, depth of circulation and geochemical evolution have been conceptualized. The groundwater flow continuity between the high rainfall plateau bounding the rift and the rift valley aquifers depends principally on the nature of the bounding faults. Up to 50% of recharge to the rift aquifers comes from the plateau as groundwater inflow where the rift is cross cut by transverse fault zones. Recharge from the mountains is found to be insignificant where the rift is bounded by marginal grabens; channel loss and local precipitation are the principal sources of recharge to the rift aquifers in such cases. At a regional scale, there is a clear zonation in the geochemical compositions of groundwaters, the result of aquifer matrix composition differences. The environmental isotope results show that the majority of the aquifers contain modern groundwaters. In a few localities, particularly in thermal groundwaters representing deeper circulation, palaeo-groundwaters have been identified. Deeper groundwaters in the rift floor have a uniform ¹⁴C age ranging between 2,300 and 3,000 years.     

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.     

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.     

Impacts of agricultural irrigation recharge on groundwater quality in a basalt aquifer system (Washington, USA): a multi-tracer approach

Irrigation in semi-arid agricultural regions can have profound effects on recharge rates and the quality of shallow groundwater. This study coupled stable isotopes (²??, ¹⁸O), age-tracers (³H, CFCs, ¹⁴C), ⁸⁷Sr/⁸⁶Sr ratios, and elemental chemistry to determine the sources, residence times, and flowpaths of groundwater and agricultural contaminants (e.g. NO ₃ ^?C ) in the Saddle Mountains Basalt Aquifer in central Washington, USA, where over 80% of the population depend on groundwater for domestic use. Results demonstrate the presence of two distinct types of water: contaminated irrigation water and pristine regional groundwater. Contaminated irrigation water has high NO ₃ ^?C concentrations (11?C116? mg/l), ⁸⁷Sr/⁸⁶Sr ratios (0.70659?C0.71078) within range of nitrogen-based fertilizers, detectable tritium (2.8?C13.4 TU), CFC ages 20?C40?years, high ??¹⁸O values (?16.9 to ?13.5??), and ??100 percent modern ¹⁴C. Pristine regional groundwater has low NO ₃ ^?C concentrations (1?C5? mg/l), no detectable tritium (??0.8 TU), low ??¹⁸O values (?18.9 to ?17.3??) and ¹⁴C ages from ??15 to 33?ky BP. Nitrogen and oxygen isotopes of NO ₃ ^?C , combined with high dissolved oxygen values, show that denitrification is not an important process in the organic-poor basalt aquifers resulting in transport of high NO ₃ ^?C irrigation water to depths greater than 40?m in less than 30? years.     

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 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.     

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.     

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.     

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.     

Fluoride enrichment mechanism and geospatial distribution in the volcanic aquifers of the Middle Awash basin,Northern Main Ethiopian Rift

Considering the anomalous concentration of fluoride in the ground waters of the Middle Awash basin, a comprehensive survey of the enrichment mechanism as well as its association with common hydrochemical variables was conducted using multivariate statistical methods, Hierarchal Cluster Analysis (HCA) and Principal Component Analysis (PCA). The HCA results indicate a marked heterogeneous spatial distribution of the fluoride concentration, the magnitude of which varies more gradually in the SSW–NNE direction along the Wonji Fault Belt (WFB) than it does in the E-W direction away from this belt. This is strongly associated with the geothermal anomaly that is prominent in the basin interior area. Furthermore, the PCA results show that the magnitude of the fluoride concentration is higher in the groundwater derived from non-calcium bearing aquifers, which are widely distributed in the rift floor. Hydrochemical processes involving a cation exchange reaction cause a systematic Ca²⁺ removal from solution from highland towards the rift floor. This geochemical reaction enhances the fluoride enrichment of groundwater along the same flow direction. In this regard, the geothermal belt of the basin interior area is a hydrogeological block marked by high loads of fluoride whereas the plateau areas are low-fluoride zones. The geospatial distribution of fluoride at the basin scale was estimated using the kriging procedure. Appropriate discrimination between local and regional aquifers is important in order to secure low-fluoride water supply for the community in the basin.     

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.     

Isotope Geochemistry of Groundwater from Fractured Dolomite Aquifers in Central Slovenia

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

The origin of groundwater arsenic and fluorine in a volcanic sedimentary basin in central Mexico: a hydrochemistry hypothesis

A groundwater sampling campaign was carried out in the summer of 2013 in a low-temperature geothermal system located in Juventino Rosas (JR) municipality, Guanajuato State, Mexico. This groundwater presents high concentrations of As and F^? and high Rn counts, mainly in wells with relatively higher temperature. The chemistry of major elements was interpreted with different methods, like Piper and D’Amore diagrams. These diagrams allowed for classification of four groundwater types located in three hydrogeological environments. The aquifers are hosted mainly in alluvial-lacustrine sediments and volcanic rocks in interaction with fault and fracture systems. The subsidence, faults and fractures observed in the study area can act as preferential channels for recharge and also for the transport of deep fluids to the surface, especially in the basin plain. The formation of a piezometric dome and the observed hydrochemical behavior of groundwater suggest a possible origin of the As and F^?. Geochemical processes occurring during water–rock interaction are related to high concentrations of As and F^?. High temperatures and alteration processes (like rock weathering) induce dissolution of As and F^?-bearing minerals, increasing the content of these elements in groundwater.     

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.     

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

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

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

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

A geochemical investigation of hydrologically derived threats to rare biota: the Drummond Nature Reserve, Western Australia

The Drummond Nature Reserve (DNR), a high-value conservation area 100?km northeast of Perth, Western Australia, contains two rare freshwater claypans and a diverse range of rare and threatened vascular plants. Groundwater/surface-water interactions were investigated via isotopic (??¹⁸O and ??D) and major ion analysis. The groundwater chemical and isotope analyses combined with nutrient data allowed for the assessment of potential hydrologically derived threats to the claypans and their associated conservation values. Groundwater composition is typically Na?CCl to Na?CMg?CCl; whereas the claypan??s ephemeral fresh surface water is Na?CCl?CHCO₃. Distinct ??¹⁸O and ??D isotopic signatures for the claypan surface waters and adjoining groundwaters indicate that there currently is minimal connection between these two hydrological systems. Hence the current threat to the freshwater claypans and associated biota from rising saline and acidic groundwater is minimal. Elevated nutrient (N) levels identified in groundwaters along the reserve??s western boundary may be linked to fertiliser regimes employed in adjoining agricultural lands. The ecosystem associated with the southwest claypan is particularly vulnerable to N and P inputs via surface-water flows, which could cause algal blooms, vegetation degradation and weed infestation.     

Natural background levels for some ions in groundwater of the Campania region (southern Italy)

The aim of the study was the determination of the natural background levels (NBLs) for the ions Na⁺, Cl^?, SO₄ ^2?, As³⁺, F^?, Fe²⁺, and Mn²⁺, in some groundwater bodies of the Campania region (southern Italy). The ??Protocol to evaluate the natural background concentrations?? proposed in 2009 by ISPRA (Italian Institute for Environmental Protection and Research) has been applied to the chemical data set of groundwater of the examined groundwater bodies. These analyses have also been examined following the guidelines of the BRIDGE project (Background cRiteria for the IDentification of Groundwater thrEshold). These approaches to evaluate the Threshold Values (TVs) and the NBLs, based on probability distribution functions, have been applied in many countries by various authors during the last 5?years. Changes applied to ISPRA Protocol in this study concern mainly the preselection criteria, in particular threshold values of specific ions, deriving from the aquifers geochemical features. The preselection criteria of the ISPRA Protocol have been merged with those of the BRIDGE Project in order to define a procedure suitable for the definition of the NBLs in the examined aquifers. The NBL of fluoride for the ??Phlegrean Fields?? and the ??eastern Plain of Naples?? groundwater bodies shows values deeply exceeding the reference value (REF) of 1,500???g/L, ranging between 3,600 and 15,000???g/L. The cause of this very high fluoride content is in the natural features of the aquifers constituted by volcanic and pyroclastic rocks. The volcanic origin of the aquifers is also the reason for the high arsenic content in ??Phlegrean Fields?? groundwater. Here the NBL calculated was about 47???g/L against the drinking water standard value of 10???g/L. The widespread high content of manganese and iron for the groundwater body of the ??eastern Plain of Naples?? is due to the reducing conditions related to the extensive marshlands present in the past. The very high NBL of all the examined ions for the groundwater body of ??Ischia Island?? depends on the existence of a geothermal system.     

Mobilisation of arsenic and other trace elements in fluviolacustrine aquifers of the Huhhot Basin,Inner Mongolia

Observed As concentrations in groundwater from boreholes and wells in the Huhhot Basin of Inner Mongolia, northern China, range between <1 μg l⁻¹ and 1480 μg l⁻¹. The aquifers are composed of Quaternary (largely Holocene) lacustrine and fluvial sediments. High concentrations are found in groundwater from both shallow and deep boreholes as well as from some dug wells (well depths ranging between <10 m and 400 m). Populations from the affected areas experience a number of As-related health problems, the most notable of which are skin lesions (keratosis, melanosis, skin cancer) but with internal cancers (lung and bladder cancer) also having been reported. In both the shallow and deep aquifers, groundwaters evolve down the flow gradient from oxidising conditions along the basin margins to reducing conditions in the low-lying central part of the basin. High As concentrations occur in anaerobic groundwaters from this low-lying area and are associated with moderately high dissolved Fe as well as high Mn, NH₄, dissolved organic C (DOC), HCO₃ and P concentrations. Many of the deep groundwaters have particularly enriched DOC concentrations (up to 30 mg l⁻¹) and are often brown as a result of the high concentrations of organic acid. In the reducing groundwaters, inorganic As(III) constitutes typically more than 60% of the total dissolved As. The highest As concentrations tend to be found in groundwater with low SO₄ concentrations and indicate that As mobilisation occurs under strongly reducing conditions, where SO₄ reduction has been an active process. High concentrations of Fe, Mn, NH₄, HCO₃ and P are a common feature of reducing high-As groundwater provinces (e.g. Bangladesh, West Bengal). High concentrations of organic acid (humic, fulvic acid) are not a universal feature of such aquifers, but have been found in groundwaters from Taiwan and Hungary for example. The observed range of total As concentrations in sediments is 3–29 mg kg⁻¹ (n=12) and the concentrations correlate positively with total Fe. Up to 30% of the As is oxalate-extractable and taken to be associated largely with Fe oxides. The release of As into solution under the reducing conditions is believed to be by desorption coupled with reductive dissolution of the Fe oxide minerals. The association of dissolved As with constituents such as HCO₃, DOC and P may be a coincidence related to the prevalent reducing conditions and slow groundwater flow, but they may also be directly involved because of their competition with As for binding sites on the Fe oxides. The Huhhot groundwaters also have some high concentrations of dissolved U (up to 53 μg l⁻¹) and F⁻ (up to 6.8 mg l⁻¹). In contrast to As, U occurs predominantly under the more oxidising conditions along the basin margins. Fluoride occurs dominantly in the shallow groundwaters which have Na and HCO₃ as the dominant ions. The combination of slow flow of groundwater and the young age of the aquifer sediments are also considered potentially important causes of the high dissolved As concentrations observed as the sediments are likely to contain newly-formed and reactive minerals and have not been well flushed since burial.     

Hydrological characteristics of karstic groundwater in the northeast Viet Nam as studied by isotopic techniques

The stable water isotopic composition (δ²H and δ¹⁸Ο), tritium (³H) activity, dissolved organic carbon, alkalinity, as well as the composition of carbon 13 (δ¹³C) in dissolved inorganic carbon (DIC) of 36 water samples taken from 16 resurgences in the northeast provinces of Viet Nam in the dry (Mar 2008) and rainy (June 2008) seasons were analyzed to elucidate hydrological characteristics of the karstic aquifers in the area. The stable water isotopic composition of the water samples collected clearly demonstrated that the karstic groundwater in the region was recharged from the local meteorological water. The tritium activity in the samples was found to be in between 3 and 4 TU, falling in the range of the ³H activity in the local precipitation and thus meaning that the traveling of recharge water to the resurgences was very short. Concentrated and diffuse allogenic recharges seem to be important sources of karstic groundwater in the study region. Water in the karstic aquifers could be classified into three types as: (a) water from karstic areas with dense vegetation cover that causes DIC be depleted in carbon 13 (¹³δ<?12‰ vs. Pee Dee Belemnite standard of Vienna, VPDB); (b) water from karstic areas with poor vegetation cover that originates DIC with carbon 13 composition ranging from ?11 to ?12‰; and (c) surface water from lakes, springs and rivers that has DIC with enriched carbon 13 (δ¹³C >?10‰). This implies that there are several sources of carbon dioxide contributing to the DIC in water of the karstic aquifers in the study region. Among other potential sources, the atmospheric CO₂, CO₂ from carbonate rock dissolution, biomineralization of soil organic matters and plant roots respiration seem to be important sources of the DIC in the waters of this region. The results show high vulnerability towards anthropogenic contaminants of karstic groundwater in the study region.