Abstract: The prospect of unconventional shale gas development in the semi-arid Karoo Basin (South Africa) has created the prerequisite to temporally characterise the natural radioactivity in associated groundwater which is solely depended on for drinking and agriculture purposes. Radon (222Rn) was the primary natural radionuclide of interest in this study; however, supplementary radium (226Ra and 228Ra) in-water measurements were also conducted. A total of 53 aquifers spanning three provinces were studied during three separate measurement campaigns from 2014 to 2016. The Karoo Basin’s natural radon-in-water levels can be characterised by a minimum of 1 ± 1 Bq/L (consistent with zero or below LLD), a maximum of 183 ± 18 Bq/L and mean of 41 ± 5 Bq/L. The mean radon-in-water levels for shallow aquifers were systematically higher (55 ± 10 Bq/L) compared to deep (14 ± 3 Bq/L) or mixed aquifers (20 ± 6 Bq/L). Radon-in-water activity concentration fluctuations were predominantly observed from shallow aquifers compared to the generally steady levels of deep aquifers. A collective seasonal mean radon-in-water levels increase from the winter of 2014 (44 ± 8 Bq/L) to winter of 2016 (61 ± 16 Bq/L) was noticed which could be related to the extreme national drought experienced in 2015. Radium-in-water (228Ra and 226Ra) levels ranged from below detection level to a maximum of 0.008 Bq/L (226Ra) and 0.015 Bq/L (228Ra). The 228Ra/226Ra ratio was characterised by a minimum of 0.93, a maximum of 6.5 and a mean value of 3.3 ± 1.3. Developing and improving baseline naturally occurring radionuclide groundwater databases is vital to study potential radiological environmental impacts attributed to industrial processes such as hydraulic fracturing or mining.

Abstract: The quantification of groundwater resources is essential especially in water scarce countries like Namibia. The chloride mass balance (CMB) method and isotopic composition were used in determining groundwater recharge along a precipitation gradient at three sites, namely: Tsumeb (600 mm/a precipitation); Waterberg (450 mm/a precipitation) and Kuzikus/Ebenhaezer (240 mm/a precipitation). Groundwater and rainwater were collected from year 2016–2017. Rainwater was collected monthly while groundwater was collected before, during and after rainy seasons. Rainwater isotopic values for δ18O and δ2H range from −10.70 to 6.10‰ and from −72.7 to 42.1‰ respectively. Groundwater isotopic values for δ18O range from −9.84 to −5.35‰ for Tsumeb; from −10.85 to −8.60‰ for Waterberg and from −8.24 to −1.56‰ for Kuzikus/Ebenhaezer, while that for δ2H range from −65.6 to −46.7‰ for Tsumeb; −69.4 to −61.2‰ for Waterberg and −54.2 to −22.7‰ for Kuzikus/Ebenhaezer. Rainwater scatters along the GMWL. Rainwater collected in January, February and March are more depleted in heavy isotopes than those in November, December, April and May. Waterberg groundwater plots on the GMWL which indicates absence of evaporation. Tsumeb groundwater plots on/close to the GMWL with an exception of groundwater from the karst Lake Otjikoto which is showing evaporation. Groundwater from Kuzikus/Ebenhaezer shows an evaporation effect, probably evaporation occurs during infiltration since it is observed in all sampling seasons. All groundwater from three sites plot in the same area with rainwater depleted in stable isotopic values, which could indicates that recharge only take place during January, February and March. CMB method revealed that Waterberg has the highest recharge rate ranging between 39.1 mm/a and 51.1 mm/a (8.7% – 11.4% of annual precipitation), Tsumeb with rates ranging from 21.1 mm/a to 48.5 mm/a (3.5% – 8.1% of annual precipitation), and lastly Kuzikus/Ebenhaezer from 3.2 mm/a to 17.5 mm/a (1.4% – 7.3% of annual precipitation). High recharge rates in Waterberg could be related to fast infiltration and absence of evaporation as indicated by the isotopic ratios. Differences in recharge rates cannot only be attributed to the precipitation gradient but also to the evaporation rates and the presence of preferential flow paths. Recharge rates estimated for these three sites can be used in managing the savannah aquifers especially at Kuzikus/Ebenhaezer where evaporation effect is observed that one can consider rain harvesting.

Abstract: The recharge of stream water below the baseflow water table can mobilize groundwater contaminants, particularly redox-sensitive and sorptive metals such as uranium. However, in-situ tracer experiments that simulate the recharge of stream water to uranium-contaminated groundwater are lacking, thus limiting the understanding of the potential mechanisms that control the mobility of uranium at the field scale. In this study, a field tracer test was conducted by injecting 100 gal (379 l) of oxic river water into a nearby suboxic and uranium-contaminated aquifer. The traced river water was monitored for 18 days in the single injection well and in the twelve surrounding observation wells. Mobilization of uranium from the solid to the aqueous phase was not observed during the tracer test despite its pre-test presence being confirmed on the aquifer sediments from lab-based acid leaching. However, strong evidence of oxidative immobilization of iron and manganese was observed during the tracer test and suggested that immobile uranium was likely in its oxidized state as U(VI) on the aquifer sediments; these observations ruled out oxidation of U(IV) to U(VI) as a potential mobilization mechanism. Therefore, desorption of U(VI) appeared to be the predominant potential mobilization mechanism, yet it was clearly not solely dependent on concentration as evident when considering that uranium-poor river water (\textless0.015 mg/L) was recharged to uranium-rich groundwater (≈1 mg/L). It was possible that uranium desorption was limited by the relatively higher pH and lower alkalinity of the river water as compared to the groundwater; both factors favor immobilization. However, it was likely that the immobile uranium was associated with a mineral phase, as opposed to a sorbed phase, thus desorption may not have been possible. The results of this field tracer study successfully ruled out two common mobilization mechanisms of uranium: (1) oxidative dissolution and (2) concentration-dependent desorption and ruled in the importance of advection, dispersion, and the mineral phase of uranium.

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.

Abstract: The solubility of uranium in groundwater is very sensitive to changes in redox conditions. Many secondary (sandstone-type) uranium deposits have been formed when soluble U has precipitated after encountering reducing conditions in the subsurface. In the groundwater of the Uitenhage Aquifer (Cape Province, South Africa), 238U-series isotopes were used to assist in studying the history of the reducing barrier. Uranium isotopes were used to determine the present position of the barrier. Radium and radon were used to evaluate the path of migration that the front of the oxygen depletion zone has taken over the past 105 years. During this time the reducing barrier has moved, leaving in its wake a trail of U in various stages of secular equilibrium with its daughter 230Th. The 226Ra daughter of 230Th is not very mobile. Its growth upon the aquifer wall is reflected in the Rn content of the water. This in turn, due to the relatively great age of the water, indicates the extent of the 230Th ingrowth (from precipitated U) that took place before the barrier migrated.