Abstract: In Situ Recovery (ISR) is the most important process of uranium production in the world (50%). It consists of an injection of a leaching solution into a permeable mineralized aquifer (sandstone), pumping of the solution after dissolution of the ore minerals and recovery of the uranium from the pregnant solution in a surface plant. In this context, the fate of swelling clay minerals such as smectites is of main importance due to their role in the mobility of cationic elements by diverse geochemical processes such as ion-exchange reactions or dissolution. The present study details analysis of dioctahedral smectites before and after in-situ leaching by acidic (H2SO4) ISR solutions. Samples were collected from two sedimentary basins hosting some of the main uranium roll front deposits exploited by acidic ISR (Tortkuduk deposit, Shu-Saryssu basin, Kazakhstan, and Dulaan Uul and Zoovch Ovoo deposits, Sainshand basin, Mongolia). Scanning Electron Microscope and X-Ray Diffraction analysis revealed that dioctahedral smectite is a ubiquitous mineral in all analyzed samples, before and after acidification, and revealed a difference of crystal chemistry of the smectites between deposits of Kazakhstan (beidellite type) and Mongolia (montmorillonite type). Chemical analysis and semi-quantification of the smectites before and after acidification also revealed a difference in chemical reactivity, with a higher dissolution of montmorillonite layers compared to beidellite ones, and the importance of ion-exchange reactions. These findings are consistent with literature data obtained on model systems. The persistence of dioctahedral smectites after several years of acidification is crucial for the understanding of geochemical processes during uranium production or remediation of the aquifers. Finally, based on the analysis of samples from U-deposits hosted in both sedimentary basins, a schematic model of the impact of acid solutions on dioctahedral smectite was proposed.

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).