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.

Abstract: More than 4,000 sandstone-hosted uranium occurrences host over 1.2 billion pounds of mined and in situ U3O8 throughout the Colorado Plateau. Most of the resources are in two distinct mineral systems with deposits hosted in the Triassic Chinle and Jurassic Morrison Formations. In the Chinle mineral system, base metal sulfides typically accompany mineralization. The Morrison mineral system is characterized by V/U ratios up to 20. The uranium source was likely volcanic ash preserved as bentonitic mudstones in the Brushy Basin Member of the Morrison Formation, and lithic volcanic clasts, ash shards, and bentonitic clay in the lower part of the Chinle Formation. Vanadium originated from two possible sources: iron–titanium oxides that are extensively altered in bleached rock near deposits or from similar minerals in variably bleached red beds interbedded with and beneath the Morrison. In Chinle-hosted deposits, in addition to volcanic ash, a contributing source of both vanadium and uranium is proposed here for the first time to be underlying red beds in the Moenkopi and Cutler Formations that have undergone a cycle of reddening-bleaching-reoxidation. Transport in both systems was likely in groundwater through the more permeable sandstones and conglomerate units. The association of uranium minerals with carbonate and more rarely apatite, suggests that transport of uranium was as a carbonate or phosphate complex. The first comprehensive examination of paleoclimate, paleotopography, and subsurface structure of aquifers coupled with analysis of the geochronology of deposits suggests that that there were distinct pulses of uranium mineralization/redistribution during the period from about 259 Ma to 12 Ma when oxidized mineralizing fluids were intermittently rejuvenated in the Plateau in response to changes in tectonic regime and climate. Multiple lines of evidence indicate that deposits formed at ambient temperatures of about 25 °C to no greater than about 140 °C. In both systems, deposits formed where groundwater flow slowed and was subject to evaporative concentration. Stagnant conditions allowed for prolonged interaction of U- and V-enriched groundwater with ferrous iron-bearing reductants, such as illite and iron–titanium oxides, and more rarely organic material such as plant debris. Paragenetically late in the sequence, reducing fluids introduced additional organic matter to some deposits. Reducing fluids and introduced organic matter (now amorphous and altered by radiolysis) may originate from regional petroleum systems where peak oil and gas generation was from ∼ 82 to ∼ 5 Ma. Our novel analysis indicates that these reducing fluids bleached rock and protected affected deposits from remobilization during exposure and weathering that followed uplift of the Plateau (∼80 to 40 Ma).

Abstract: Groundwater resources in the crystalline basement complex of India are crucial for supplying drinking water in both rural and urban settings. Groundwater depletion is recognised as a challenge across parts of India due to over-abstraction, but groundwater quality constraints are perhaps even more widespread and often overlooked at the local scale. Uranium contamination in basement aquifers has been reported in many parts of India, locally exceeding WHO drinking water guideline values of 30 μg/L and posing a potential health risk. In this study 130 water samples were collected across three crystalline basement catchments to assess hydrochemical, geological and anthropogenic controls on uranium mobility and occurrence in drinking water sources. Groundwaters with uranium concentrations exceeding 30 μg/L were found in all three study catchments (30% of samples overall), with concentrations up to 589 μg/L detected. There appears to be a geological control on the occurrence of uranium in groundwater with the granitic gneiss of the Halli and Bengaluru study areas having higher mean uranium concentrations (51 and 68 μg/L respectively) compared to the sheared gneiss of the Berambadi catchment (6.4 μg/L). Uranium – nitrate relationships indicate that fertiliser sources are not a major control on uranium occurrence in these case studies which include two catchments with a long legacy of intense agricultural land use. Geochemical modelling confirmed uranium speciation was dominated by uranyl carbonate species, particularly ternary complexes with calcium, consistent with uranium mobility being affected by redox controls and the presence of carbonates. Urban leakage in Bengaluru led to low pH and low bicarbonate groundwater hydrochemistry, reducing uranium mobility and altering uranium speciation. Since the majority of inhabitants in Karnataka depend on groundwater abstraction from basement aquifers for drinking water and domestic use, exposure to elevated uranium is a public health concern. Improved monitoring, understanding and treatment of high uranium drinking water sources in this region is essential to safeguard public health.

Abstract: This study refines the hydrogeological conceptual model of an area with three interconnected aquifers, namely the Crystalline Aquifer System (CAS – igneous and metamorphic rocks), which is in contact with the Tubarão Aquifer System (TAS – sedimentary rocks) and the Diabase Aquifer System (DAS – diabase rocks). The detailed investigation involved geophysical logging and hydraulic and hydrodynamic characterization with straddle packers in a local tubular well, in which groundwater presents high uranium concentrations. Hydrogeochemical and isotope (δ2H, δ18O, 3H, δ13C, 14C) analysis in this well and in other three neighboring wells, with lower U concentrations, showed that ancient and modern waters (3H from <0.8 to 1.12 TU, 14C from 69.43 to 78.72 pMC) mix within the aquifer. During groundwater pumping, vertical fractures in the diabase aquifer possibly induce water mixing and recharge of the deeper levels of the aquifers from shallow layers. The high [U] are related to ancient waters from a confined aquifer hosted in CAS that reaches the wells through hydraulically active fractures located deeper than 159 m depth. Groundwater apparent ages do not increase systematically with depth, revealing a complex circulation model for CAS. The results obtained from the other wells, which are all located on drainage lineaments, reveal that one extracts modern water from DAS and TAS, another one extracts modern and ancient water from DAS and CAS, and the third extracts only ancient water from CAS, confirming the complexity of the local hydrogeology. Regarding regional groundwater management, the study revealed the need to characterize the sources of groundwater in each well, in order to protect modern waters from anthropogenic contamination and to protect ancient groundwater from overexploitation, as CAS hosts groundwaters recharged thousands of years ago or more.

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.