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: 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: Despite numerous studies, there are many knowledge gaps in our understanding of uranium (U) contamination in the alluvial aquifers of Punjab, India. In this study, a large hydrogeochemical dataset was compiled to better understand the major factors controlling the mobility and enrichment of uranium (U) in this groundwater system. The results showed that shallow groundwaters (\textless60 m) are more contaminated with U than from deeper depths (\textgreater60 m). This effect was predominant in the Southwest districts of the Malwa, facing significant risk due to chemical toxicity of U. Groundwaters are mostly oxidizing and alkaline (median pH: 7.25 to 7.33) in nature. Spearman correlation analysis showed that U concentrations are more closely related to total dissolved solids (TDS), salinity, Na, K, HCO3−, NO3− Cl−, and F− in shallow water than deep water, but TDS and salinity remained highly correlated (U-TDS: ρ = 0.5 to 0.6; U-salinity: ρ = 0.5). This correlation suggests that the salt effect due to high competition between ions is the principal cause of U mobilization. This effect is evident when the U level increased with increasing mixed water species (Na-Cl, Mg-Cl, and Na-HCO3). Speciation data showed that the most dominant U species are Ca2UO2(CO3)2− and CaUO2(CO3)3−, which are responsible for the U mobility. Based on the field parameters, TDS along with pH and oxidation-reduction potential (ORP) were better fitted to U concentration above the WHO guideline value (30 μg.L−1), thus this combination could be used as a quick indicator of U contamination. The strong positive correlation of U with F− (ρ = 0.5) in shallow waters indicates that their primary source is geogenic, while anthropogenic factors such as canal irrigation, groundwater table decline, and use of agrochemicals (mainly nitrate fertilizers) as well as climate-related factors i.e., high evaporation under arid/semi-arid climatic conditions, which result in higher redox and TDS/salinity levels, may greatly affect enrichment of U. The geochemical rationale of this study will provide Science-based-policy implications for U health risk assessment in this region and further extrapolate these findings to other arid/semi-arid areas worldwide.

Abstract: With its arid and semi-arid climate, Iran claims about one-third of the world’s average annual precipitation. Accordingly, the present study investigated whether an effective water resources management (WRM) strategy (both groundwater and reservoir resources) could reduce groundwater drawdown while simultaneously providing secure enough water for preservation of agricultural activities and rural settlements. For this purpose, a comprehensive system dynamics (SD) model incorporating reservoir, surface-water, and groundwater resources was developed. Then, the model was implemented for the Nesa plain in Bam County, Iran, as an example. In this plain, the construction of a dam to supply drinking water to the cities of Bam and the Bam Industrial Zone had devastated the environment and human communities in the downstream areas, leading to the depopulation of as many as 104 villages in the Bam region. The results of the SD model revealed that the artificial recharge of the plain groundwater aquifer along with the management of the operation of the wells and increasing productivity would be very effective. In order to estimate future precipitation data, the SDSM statistical exponential microscale model was used to microscale the large CanESM2 scale model under two scenarios of RCP4.5 and RCP8.5. The continuation of the current trend of the groundwater resources in the plain during the next 20 years will also cause a drop in water level of 8.3 m compared with the existing situation and a reduction of 41 m compared with the long-term average of 1980. Based on this modeling effort, upon releasing 60% of river flow, surplus to downstream demand, for recharging aquifer through artificial recharge projects, the rate of water table fall will decline significantly over a 20-year period and the amount of negative aquifer water balance would most likely improve from 65.5 to 35.17 million cubic meters annually.