Abstract: Previous research on lacustrine stromatolites from Etosha Pan in Namibia obtained ages on carbonate close to or beyond the limits of radiocarbon dating. These ages suggested that the basin was likely not subject to extensive flooding during the last ca. 40ka. This study shows that AMS radiocarbon ages for the carbonate of a stromatolite from Poacher’s Point are 15–21ka older than ages for organic material in the stromatolite structure. Calibrated ages range from 30 to 40ka for carbonate and 3–19ka for the organic residue. The new ages, together with petrographic and isotopic data for the stromatolite, have provided important new information on past flooding of Etosha Pan including evidence of prolonged lacustrine conditions during the Holocene Climatic Optimum.

Abstract: This paper studies the uranium content and uranium isotopic disequilibria as a tool to identify hydrogeochemical processes from 52 groundwater samples in the province of Granada (Betic Cordillera, southeastern Spain). According to the geological complexity of the zone, three groups of samples have been considered. In Group 1 (thermal waters; longest residence time), the average uranium content was 2.63 ± 0.16 μg/L, and 234U/238U activity ratios (AR) were the highest of all samples, averaging 1.92 ± 0.30. In Group 2 (mainly springs from carbonate aquifers; intermediate residence time), dissolved uranium presented an average value of 1.34 ± 0.13 μg/L, while AR average value was 1.38 ± 0.25. Group 3 comes from pumping wells in a highly anthropized alluvial aquifer. In this group, where the residence time of the groundwater is the shortest of the three, average uranium content was 5.28 ± 0.26 μg/L, and average AR is the lowest (1.17 ± 0.12). In addition, the high dissolved uranium value and the low AR brought to light the contribution of fertilizers (Group 3). In the three groups, 235U/238U activity ratios were similar to the natural value of 0.046. Therefore, 235U detected in the samples comes from natural sources. This study is completed with the determination of major ions and physicochemical parameters in the groundwater samples and the statistical analysis of the data by using the Principal Component Analysis. This calculation indicates the correlation between uranium isotopes and bicarbonate and nitrate anions.

Abstract: Generic hydrochemical modelling of a grantoid-groundwater system, using the Russian software “HydroGeo”, has been carried out with an emphasis on simulating the accumulation of uranium in the aqueous phase. The baseline model run simulates shallow granitoid aquifers (U content 5 ppm) under conditions broadly representative of southern Norway and southwestern Siberia: i.e. temperature 10 °C, equilibrated with a soil gas partial CO2 pressure (PCO2, open system) of 10−2.5 atm. and a mildly oxidising redox environment (Eh = +50 mV). Modelling indicates that aqueous uranium accumulates in parallel with total dissolved solids (or groundwater mineralisation M – regarded as an indicator of degree of hydrochemical evolution), accumulating most rapidly when M = 550–1000 mg L−1. Accumulation slows at the onset of saturation and precipitation of secondary uranium minerals at M = c. 1000 mg L−1 (which, under baseline modelling conditions, also corresponds approximately to calcite saturation and transition to Na-HCO3 hydrofacies). The secondary minerals are typically “black” uranium oxides of mixed oxidation state (e.g. U3O7 and U4O9). For rock U content of 5–50 ppm, it is possible to generate a wide variety of aqueous uranium concentrations, up to a maximum of just over 1 mg L−1, but with typical concentrations of up to 10 μg L−1 for modest degrees of hydrochemical maturity (as indicated by M). These observations correspond extremely well with real groundwater analyses from the Altai-Sayan region of Russia and Norwegian crystalline bedrock aquifers. The timing (with respect to M) and degree of aqueous uranium accumulation are also sensitive to Eh (greater mobilisation at higher Eh), uranium content of rocks (aqueous concentration increases as rock content increases) and PCO2 (low PCO2 favours higher pH, rapid accumulation of aqueous U and earlier saturation with respect to uranium minerals).

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.