Abstract: This study combines historical records of 14C and 3H in the atmosphere and soil with renewal rate and groundwater lumped parameter models to predict the abundance of 14C and 3H in groundwater over time. 624 groundwater samples from numerous studies, over four decades (1978–2019), in South Africa, Namibia, Botswana and Mozambique were collated to compare with predicted groundwater activities of 14C and 3H within the South African Development Community (SADC) region. Spatial datasets of carbonate bearing lithology, C3/C4 vegetation, summer/winter rainfall and coastal proximity were used to apply corrections to 14C and 3H data. Corrected values of 14C and 3H were compared with the theoretical abundance of these tracers, derived from the lumped parameter models, to estimate the general mean residence times and presence of groundwater mixing between modern recharge and older groundwaters. This study found that corrected values produced varying mean residence times derived from 14C ages (∼500–28500 years) and a wide range of potentially mixed waters within each aquifer system (0–100 % of tested wells) across the study area. The largest proportions of mixed groundwater, as well as the youngest mean residence times, were found in alluvial and primary fractured rock aquifers (e.g., western coast of South Africa and southern Mozambique). The smallest proportions of mixed groundwater were predicted in deep confined clay-rich aquifers as well as layered coal bearing carbonate sequences (e.g., Orapa, Malwewe and Serowe, Botswana). Insights into the proportions of mixed groundwater and mean residence times can help assess hydrological resilience on a regional scale. Such information is pertinent in promoting socio-economic development and increased water/food security in the SADC region. By understanding the resilience of groundwater resources, robust and informed strategies for water equality and GDP growth in the SADC region can be envisioned and implemented.

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 sandstone-hosted uranium mineralization areas in the Sanzhao Sag of the northern Songliao Basin have been newly identified. The target stratum is the Upper Cretaceous Sifangtai Formation and the uranium mineralization mainly occurs in the bottom of Sifangtai Formation, corresponding to channel sand bodies in meandering river system, characterized by medium to fine-grained sandstone. This study proposes the uranium metallogenic model through petrographic observation, whole rock geochemistry, mineralogical study of uranium occurrence form (SEM), organic matter rock–eval pyrolysis analysis (REP) and in-situ sulfur isotope determination of different generations of pyrite by LA-MC-ICP-MS. Compared with the sandstones collected in barren reduction and oxidization zones, the mineralized sandstones show obvious increase in the contents of TOC, total sulfur, Y and U. Petrographic observations indicate that organic matters are mainly inherited from land plants. REP data display that the organic matter (OM) disseminated in the sandstone has very low hydrogen index (HI) from around 0 to 21 mg HC/g TOC and varied oxygen index (OI) from 44 to 115 mg CO2/g TOC, corresponding to Type Ⅳ kerogen (degraded kerogen). There are two types of coffinite with different grain size, micro-particles (μm-sized) and large aggregates (generally up to 100 μm) respectively. The coffinite micro spherules exhibit short rod-like or worm-like morphology occurring in clay matrix and cell cavities in degradofusinite or around subidiomorphic-idiomorphic pyrite. The coarse-grained coffinite contains other mineral facies (e.g. pyrite, quartz) and some of large coffinite aggregates display thrombolite-type microbial structures. The irregular pyrite relict particles in coarse-grained colloidal coffinite have light sulfur isotope compositions characterized by δ34S values from –39.96‰ to –49.89‰. The δ34S values of colloidal pyrite in replacement of OM or of the sub-idiomorphic FeS2 cement filling in the cavities of OM range from –52.77‰ to –13.88‰. Some of sub-idiomorphic pyrite cement and idiomorphic crystal have the heavier signature from – 27.06‰ to + 14.23‰. The light sulfur isotope signature suggests that the sulfur originates from bacterial sulfate reduction (BSR). The OM replacement by pyrite and the highest OI values recorded by REP in uranium mineralized samples are lines of evidence of biodegradation. Bacteria use the organic matter as food source and produce isotopically light reduced sulfur species. Oxygenated uranium-bearing waters infiltrated through the denudated windows at Daqing placanticline into the porous reduced sandstones deposited in the Sanzhao Sag. Uranium was indirectly reduced by BSR-derived iron disulfides or directly reduced by sulfate-reducing bacteria.