Abstract: The concentrations of U in natural waters are usually low, being typically less than 4 μg/L in river water, around 3.3 μg/L in open seawater, and usually less than 5 μg/L in groundwater. Higher concentrations can occur in both surface water and groundwater and the range spans some six orders of magnitude, with extremes in the mg/L range. However, such extremes in surface water are rare and linked to localized mineralization or evaporation in alkaline lakes. High concentrations in groundwater, substantially above the WHO provisional guideline value for U in drinking water of 30 μg/L, are associated most strongly with (i) granitic and felsic volcanic aquifers, (ii) continental sandstone aquifers especially in alluvial plains and (iii) areas of U mineralization. High-U groundwater provinces are more common in arid and semi-arid terrains where evaporation is an additional factor involved in concentrating U and other solutes. Examples of granitic and felsic volcanic terrains with documented high U concentrations include several parts of peninsular India, eastern USA, Canada, South Korea, southern Finland, Norway, Switzerland and Burundi. Examples of continental sandstone aquifers include the alluvial plains of the Indo-Gangetic Basin of India and Pakistan, the Central Valley, High Plains, Carson Desert, Española Basin and Edwards-Trinity aquifers of the USA, Datong Basin, China, parts of Iraq and the loess of the Chaco-Pampean Plain, Argentina. Many of these plains host eroded deposits of granitic and felsic volcanic precursors which likely act as primary sources of U. Numerous examples exist of groundwater impacted by U mineralization, often accompanied by mining, including locations in USA, Australia, Brazil, Canada, Portugal, China, Egypt and Germany. These may host high to extreme concentrations of U but are typically of localized extent. The overarching mechanisms of U mobilization in water are now well-established and depend broadly on redox conditions, pH and solute chemistry, which are shaped by the geological conditions outlined above. Uranium is recognized to be mobile in its oxic, U(VI) state, at neutral to alkaline pH (7–9) and is aided by the formation of stable U–CO3(±Ca, Mg) complexes. In such oxic and alkaline conditions, U commonly covaries with other similarly controlled anions and oxyanions such as F, As, V and Mo. Uranium is also mobile at acidic pH (2–4), principally as the uranyl cation UO22+. Mobility in U mineralized areas may therefore occur in neutral to alkaline conditions or in conditions with acid drainage, depending on the local occurrence and capacity for pH buffering by carbonate minerals. In groundwater, mobilization has also been observed in mildly (Mn-) reducing conditions. Uranium is immobile in more strongly (Fe-, SO4-) reducing conditions as it is reduced to U(IV) and is either precipitated as a crystalline or ‘non-crystalline’ form of UO2 or is sorbed to mineral surfaces. A more detailed understanding of U chemistry in the natural environment is challenging because of the large number of complexes formed, the strong binding to oxides and humic substances and their interactions, including ternary oxide-humic-U interactions. Improved quantification of these interactions will require updating of the commonly-used speciation software and databases to include the most recent developments in surface complexation models. Also, given their important role in maintaining low U concentrations in many natural waters, the nature and solubility of the amorphous or non-crystalline forms of UO2 that result from microbial reduction of U(VI) need improved quantification. Even where high-U groundwater exists, percentage exceedances of the WHO guideline value are variable and often small. More rigorous testing programmes to establish usable sources are therefore warranted in such vulnerable aquifers. As drinking-water regulation for U is a relatively recent introduction in many countries (e.g. the European Union), testing is not yet routine or established and data are still relatively limited. Acquisition of more data will establish whether analogous aquifers elsewhere in the world have similar patterns of aqueous U distribution. In the high-U groundwater regions that have been recognized so far, the general absence of evidence for clinical health symptoms is a positive finding and tempers the scale of public health concern, though it also highlights a need for continued investigation.

Abstract: Groundwater resources in the crystalline basement complex of India are crucial for supplying drinking water in both rural and urban settings. Groundwater depletion is recognised as a challenge across parts of India due to over-abstraction, but groundwater quality constraints are perhaps even more widespread and often overlooked at the local scale. Uranium contamination in basement aquifers has been reported in many parts of India, locally exceeding WHO drinking water guideline values of 30 μg/L and posing a potential health risk. In this study 130 water samples were collected across three crystalline basement catchments to assess hydrochemical, geological and anthropogenic controls on uranium mobility and occurrence in drinking water sources. Groundwaters with uranium concentrations exceeding 30 μg/L were found in all three study catchments (30% of samples overall), with concentrations up to 589 μg/L detected. There appears to be a geological control on the occurrence of uranium in groundwater with the granitic gneiss of the Halli and Bengaluru study areas having higher mean uranium concentrations (51 and 68 μg/L respectively) compared to the sheared gneiss of the Berambadi catchment (6.4 μg/L). Uranium – nitrate relationships indicate that fertiliser sources are not a major control on uranium occurrence in these case studies which include two catchments with a long legacy of intense agricultural land use. Geochemical modelling confirmed uranium speciation was dominated by uranyl carbonate species, particularly ternary complexes with calcium, consistent with uranium mobility being affected by redox controls and the presence of carbonates. Urban leakage in Bengaluru led to low pH and low bicarbonate groundwater hydrochemistry, reducing uranium mobility and altering uranium speciation. Since the majority of inhabitants in Karnataka depend on groundwater abstraction from basement aquifers for drinking water and domestic use, exposure to elevated uranium is a public health concern. Improved monitoring, understanding and treatment of high uranium drinking water sources in this region is essential to safeguard public health.

Abstract: The origin of groundwater recharge and subsequent flow paths are often difficult to establish in fractured, multi-lithological, and highly compartmentalized aquifers such as the Troodos Fractured Aquifer (TFA). As the conjunctive use of stable isotopes and hydrogeochemical data provides additional information, we established a monitoring network for stable isotopes in precipitation in Cyprus. The local meteoric water line, altitude effect and seasonal variation of stable isotopes in precipitation are derived from monitoring data. Stable isotopes and hydrogeochemical data are combined to model water-rock interactions and groundwater evolution along a complete ophiolite sequence. As a result a generic hydrogeologic description for the observed water types is developed. Isotope hydrology was applied in conjunction with hydrogeochemical modelling in Kargiotis Watershed, a major north-south transect of the TFA. PHREEQC was used for hydrogeochemical modelling to establish generic descriptions for observed water types. Mean precipitation-weighted values from 16 monitoring stations were used to calculate the Local Meteoric Water Line (LMWL), which was found to be equal to δ2H = (6.58 ± 0.13)*δ18O + (12.64 ± 0.91). A general decrease of 1.22‰ for δ2H and 0.20‰ for δ18O in precipitation was calculated per 100 m altitude. A generic groundwater evolution path was established: 1. Na/MgClHCO3, 2. MgHCO3, 3. Ca/MgHCO3, 4. Ca/MgNaHCO3, 4a. MgNa/CaHCO3/Cl, 5. NaMg/CaHCO3/Cl, 6. NaHCO3, 7. Na/MgHCO3SO4, 8. NaSO4Cl/HCO3. Hydrogeologic descriptions, consisting of groundwater origin, flow path and possible active water-rock processes, have been realised for the observed water types. The first two water types occur in serpentine and ultramafic-gabbro springs. Type 3 waters represent early stages of recharge and/or short flow paths, in gabbro whereas types 4 and 5 are typical for further percolating waters in gabbro and diabase. Water types 6 and 7 occur both in diabase and in the basal group and represent the regional flow. Water type 8 is the end member of regional, upwelling groundwater in the basal group. The presented descriptions and methods have practical applications in groundwater exploration, characterization, and protection. The methodology can be applied in other complex aquifer systems.

Abstract: 4He concentrations in excess of the solubility equilibrium with the atmosphere by up to two to three orders of magnitude are observed in the Carrizo Aquifer in Texas, the Ojo Alamo and Nacimiento aquifers in the San Juan Basin, New Mexico, and the Auob Sandstone Aquifer in Namibia. A simple 4He accumulation model is applied to explain these excess 4He concentrations in terms of both in situ production and a crustal flux across the bottom layer of the aquifer. Results from the model simulations suggest variability in the 4He fluxes, ranging from 6×10−6 cm3 STP cm−2 yr−1 for the Auob Sandstone Aquifer to 3.6×10−7 cm3 STP cm−2 yr−1 for the Carrizo aquifer. For the Ojo Alamo and Nacimiento aquifers an intermediate value of 3×10−6 cm3 STP cm−2 yr−1 was estimated. The contribution of in-situ produced 4He to the measured concentrations was also estimated. This contribution is negligible for the Auob Sandstone Aquifer as compared with both the concentrations measured at the top and bottom of the aquifer for most of the pathway. In the Carrizo aquifer, in-situ produced 4He contributes 27.5% and 15.4%, to the total 4He observed at the top and bottom of the aquifer, respectively. For both aquifers of the San Juan Basin in-situ production almost entirely dominates the 4He concentrations at the top of the aquifer for most of the pathway. In contrast, the internal production is negligible as compared with the measured concentrations at the bottom of these aquifers, reaching, at most, 1.1%. The model simulations require an exponential decrease in the horizontal velocity of the water with increasing recharge distance to reproduce the distribution of 4He in these aquifers. For the Auob Sandstone Aquifer the highest range in the velocity values is obtained (25 to 0.4 m yr−1). The simulations for the Carrizo aquifer and both aquifers located in the San Juan Basin require velocities varying from 4 to 0.1 m yr−1, and from 2 to 0.3 m yr−1, respectively. For each aquifer, average permeability values were also estimated. They are generally in agreement with results obtained from pumping tests, hydrodynamic modeling and previous 14C measurements. On the basis of the results obtained by calibrating the model with the measured 4He concentrations, the mean water residence times were estimated. They agree reasonably well with 14C ages. When applied as chronologies for noble gas temperatures in the same aquifers, the calculated 4He ages allow the identification of three different climate periods similar to those previously identified using 14C ages: (1) the Holocene period (0–10 Ka BP), (2) the Last Glacial Maximum (≈18 Ka BP), and (3) the preceeding period (30–150 Ka BP).