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).

Abstract: Environmental hazards are caused by uranium mining legacies and enhanced radioactivity in utilized groundwater and surface water resources. Knowledge of uranium speciation in these waters is essential for predicting radionuclide migration and for installing effective water purification technology. The validity of the thermodynamic data for the environmental media affected by uranium mining legacies is of utmost importance. Therefore, a comprehensive and consistent database was established according to current knowledge. The uranium data included in the database is based on the NEA TDB (Guillaumont et al., 2003) and is modified or supplemented as necessary e.g. for calcium and magnesium uranyl carbonates. The specific ion interaction theory (Brönsted, 1922) is used to estimate activity constants, which is sufficient for the considered low ionic strengths. The success of this approach was evaluated by comparative experimental investigations and model calculations (PHREEQC (Parkhurst and Appelo, 1999)) for several model systems. The waters differ in pH (2.7–9.8), uranium concentration (10−9-10−4 mol/L) and ionic strength (0.002–0.2 mol/L). We used chemical extraction experiments, ESI-Orbitrap-MS and time-resolved laser-induced fluorescence spectroscopy (TRLFS) to measure the uranium speciation. The latter method is nonintrusive and therefore does not change the chemical composition of the investigated waters. This is very important, because any change of the system under study may also change the speciation.

Abstract: The distribution of uranium isotopes (238U and 234U) in groundwaters of the south-western margin of the Great Artesian Basin (GAB), Australia, and underlying Arckaringa Basin were examined using groundwater samples and a sequential extraction of aquifer sediments. Rock weathering, the geochemical environment and α-recoil of daughter products control the 238U and 234U isotope distributions giving rise to large spatial variations. Generally, the shallowest aquifer (J aquifer) contains groundwater with higher 238U activity concentrations and 234U/238U activity ratios close to secular equilibrium. However, the source input of uranium is spatially variable as intermittent recharge from ephemeral rivers passes through rocks that have already undergone extensive weathering and contain low 238U activity concentrations. Other locations in the J aquifer that receive little or no recharge contain higher 238U activity concentrations because uranium from localised uranium-rich rocks have been leached into solution and the geochemical environment allows the uranium to be kept in solution. The geochemical conditions of the deeper aquifers generally result in lower 238U activity concentrations in the groundwater accompanied by higher 234U/238U activity ratios. The sequential extraction of aquifer sediments showed that α-recoil of 234U from the solid mineral phases into the groundwater, rather than dissolution of, or exchange with the groundwater accessible minerals in the aquifer, caused enrichment of groundwater 234U/238U activity ratios in the Boorthanna Formation. Decay of 238U in uranium-rich coatings on J aquifer sediments caused resistant phase 234U/238U activity ratio enrichment. The groundwater 234U/238U activity ratio is dependent on groundwater residence time or flow rate, depending on the flow path trajectory. Thus, uranium isotope variations confirmed earlier groundwater flow interpretations based on other tracers; however, spatial heterogeneity, and the lack of clear regional correlations, made it difficult to identify recharge and inter-aquifer leakage.

Abstract: From 1950 through the early 1980’s New Mexico accounted for roughly half of domestic uranium (U) production for the nuclear power industry and the nation’s weapon programs. Increased interest in nuclear energy has led to proposals for renewed development using both underground mining and uranium in situ recovery (ISR). When feasible, ISR greatly reduces waste generated by the mining and milling processes, however, the ability to restore ground water to acceptable quality after ISR ends is uncertain. This research investigated two methods of stabilizing an aquifer following ISR. Batch and column studies were performed to evaluate chemical and biological methods of stabilization. Columns packed with ore were first leached with an aerated NaHCO3 ground water solution to simulate ISR. Constituents present at elevated concentrations after leaching included molybdenum (Mo), selenium (Se), U, and vanadium (V). Chemical stabilization was studied by passing a phosphate (PO43-) amended solution through the ore to achieve passivation of mineral surfaces by P precipitates. Microbial stabilization was studied by passing a lactate solution through the ore to stimulate growth of anaerobic metal- and sulfate-reducing organisms to reduce U and other elements to less soluble phases. Analyses of the solids from the columns after completion of these experiments by X-ray photo electron spectroscopy (XPS) identified phosphate on samples near the column inlet of the chemically stabilized columns. Microbial populations were characterized by Illumina DNA sequencing and confirmed the presence of metal- and sulfate-reducing organisms. Neither chemical nor microbial stabilization method achieved contaminant immobilization, which is believed due to limited mixing of the stabilization solutions with the contaminated leach solutions. These results emphasize that ground water hydrodynamics, especially mixing, must be considered in aquifer restoration of soluble constituents.

Abstract: The complex behavior of uranium in recovery is mostly driven by water-rock interactions following lixiviant injection into ore-bearing aquifers. Significant challenges exist in exploring the geochemical processes responsible for uranium release and mobilization. Herein this study provides an illustration of a ten-year field scale CO2 and O2 in-situ leaching (ISL) process at a typical sandstone-hosted uranium deposit in northern China. We also conducte a three-dimensional (3-D) multicomponent reactive transport model to assess the effects of potential chemical reactions on uranium recovery, in particular, to focus on the role of sulfide mineral pyrite (FeS2). Numerical simulations are performed considering three potential ISL reaction pathways to determine the relative contributions to uranium release, and the results indicate that bicarbonate promotes the oxidative dissolution of uranium-bearing minerals and further accelerates the uranium leaching in a neutral geochemical system. Moreover, the presence of FeS2 exerts a strong competitive role in the uranium-bearing mineral dissolution by increasing oxygen consumption, favoring the formation of iron oxyhydroxide, and therefore causing an associated decrease in uranium recovery rates. The simulation model demonstrates that dissolution of carbonate neutralizes acidic water generated from pyrite oxidation and aqueous CO2 dissociation. In addition, the cation concentrations (i.e., Ca and Mg) are increasing in the pregnant solutions, showing that the recycling of lixiviants and kinetic dissolution of carbonate generates a larger number of dissolved Ca and Mg and inevitably triggers the secondary dolomite mineral precipitation. The findings improve our fundamental understanding of the geochemical processes in a long-term uranium ISL system and provide important environmental implications for the optimal design of uranium recovery, remediation, and risk exposure assessment.