Search Results (34)

Carbonaceous–siliceous–argillaceous rock-type uranium deposits, a major uranium resource in China, pose significant environmental risks due to heavy metal contamination. Geochemical investigations in the former Zoige uranium mine revealed elevated As, Cd, Cr, Cu, Ni, U, and Zn concentrations in soils and sediments, particularly at river confluences and downstream regions, attributed to leachate migration from ore bodies and tailings ponds. Surface samples exhibited high Cd bioavailability. The integrated BCR and mineral analysis reveals that Acid-soluble and reducible fractions of Ni, Cu, Zn, As, and Pb are governed by carbonate dissolution and Fe-Mn oxide dynamics via silicate weathering, while residual and oxidizable fractions show weak mineral-phase dependencies. Positive Matrix Factorization identified natural lithogenic, anthropogenic–natural composite, mining-related sources. Pollution assessments using geo-accumulation index and contamination factor demonstrated severe contamination disparities: soils showed extreme Cd pollution, moderate U, As, Zn contamination, and no Cr, Pb pollution (overall moderate risk); sediments exhibited extreme Cd pollution, moderate Ni, Zn, U levels, and negligible Cr, Pb impacts (overall extreme risk). USEPA health risk models indicated notable non-carcinogenic (higher in adults) and carcinogenic risks (higher in children) for both age groups. Ecological risk assessments categorized As, Cr, Cu, Ni, Pb, and Zn as low risk, contrasting with Cd (extremely high risk) and sediment-bound U (high risk). These findings underscore mining legacy as a critical environmental stressor and highlight the necessity for multi-source pollution mitigation strategies. Full article

Bacillus subtilis exhibits a great affinity to soluble U(VI) through non-reducing biomineralization. The pH value, temperature, initial uranium concentration, bacterial concentration, and adsorption time are recognized as the five environmental sensitive factors that can regulate the degree of non-reductive biomineralization. Most of the current studies have focused on the regulatory mechanisms of these factors on uranium non-reductive mineralization. However, there are still few reports on the importance of these factors in influencing non-reductive mineralization, as well as on how to regulate these factors to increase the efficiency of non-reductive mineralization and enhance the enrichment of Bacillus subtilis on uranium. In this work, a deep learning neural network model was constructed to effectively predict the effects of changes in these five environmental sensitivity factors on the non-reducing mineralization of Bacillus subtilis to uranium. Accuracy (99.6%) and R² (up to 0.89) confirm a high degree of agreement between the predicted output and the observed values. Sensitivity analysis shows that in this model, pH value is the most important influencing factor. However, under different pH values, temperature, initial uranium concentration, adsorption time, and bacterial concentration have different effects. When the pH value is lower than 6, the most important factor is temperature, and once the pH value is greater than 6, the initial concentration is the most important factor. The results are expected to provide a theoretical basis for regulating the enrichment degree of U(VI) by Bacillus subtilis, achieving the maximum long-term stable fixation of U(VI), and understanding the environmental chemical behavior of uranium under different conditions. Full article

Understanding the fate of contaminants in heterogeneous aquifer systems is crucial to explain their transport behavior. Although it has been proven that heterogeneity has a significant control over the quantification of these processes, the extent of this impact is yet to be studied. The unique contribution of this work lies in the assessment of field-scale physical and chemical heterogeneity in modeling reactive transport processes in the subsurface. The main objective of this study is to investigate the impact of physical and chemical heterogeneity in understanding biogeochemical processes of contaminants in the subsurface environment, coupled with advective and dispersive transport in situ with mixing limitations. This study is particularly focused on an example of uranium, where especially coupled bioreduction and reoxidation processes in the presence of Fe (III) hydroxides are considered. For this purpose, 2D numerical biogeochemical reactive transport models are developed to simulate the fate and transport of uranium in a heterogeneously distributed subsurface. Results have shown that neglecting spatial heterogeneity might lead to an overestimation of uranium bioreduction, where physical heterogeneity has been observed to have a greater impact than chemical heterogeneity in the absence of adsorption reactions. On the other hand, when adsorption of uranium is included, the significance of chemical heterogeneity is more pronounced. Thus, when potential adsorption of contaminants is ignored or if chemical heterogeneity is ignored in the presence of adsorption reactions, the contaminant concentrations might be underestimated. The underestimation is more pronounced in low hydraulic conductivity zones due to the mixing limitations for soluble compounds, whereas for immobile phase interactions, high hydraulic conductivity regions became significant. The impact of U(IV) reoxidation process is also more pronounced in the presence of chemical heterogeneity and particularly enhanced in the zones with the highest mixing. The findings of this study can shed light on identifying the conditions that necessitate the accurate characterizations of physical and chemical heterogeneity in predicting contaminant transport with mixing limitations subject to competing biogeochemical reactions in the natural subsurface. Full article

Hydrothermal alteration provides critical information for both the exploration and scientific research of hydrothermal uranium deposits. The Xiangshan uranium ore field, the largest volcanic-hosted uranium deposit in China, is characterized by different alterations, including hematitization, illitization, sericitization, chloritization, carbonation and silicification. However, the mineralogical and geochemical characteristics of hydrothermal alterations and their relationships with uranium mineralization remain unclear. In this study, we conducted detailed petrography, TIMA mapping, μ-XRF analyses, mass balance calculations and thermodynamic modeling on the hematitized and illitized porphyritic lava from the Zoujiashan deposit in the Xiangshan ore field. During hematitization, hematite and albite are produced, while quartz, K-feldspar, chlorite, sericite and biotite are consumed, consistent with the increase in Na₂O, Al₂O₃, Fe₂O₃-T, U, As, Pb, Cu, Sc, V, Zr, Y, Hf and Th and the loss of K₂O, MgO, Li, Zn, Ni and Ba. The production of hydrothermal hematite, illite and sericite indicates that the ore fluids are acidic and oxidized. Such physiochemical conditions are favorable for uranium transport as UO₂Cl₂(aq), UO₂SO₄(aq) and UO₂OH⁺. Geological processes such as fluid–rock interactions, fluid mixing and fluid boiling could cause fO₂(g) decrease, pH increase and temperature decrease and therefore result in the decrease in uranium solubility and mineralization. Full article

Rhenium is an extremely rare critical metal element in Earth’s continental crust. Owing to its extremely high melting point and heat-stable crystalline structure, rhenium is an essential component of alloy materials used in high-performance aircraft engines. Demand for rhenium resources is therefore growing. Currently, most rhenium is produced as a byproduct of molybdenum mining in porphyry copper–molybdenum deposits. Research has therefore focused on the enrichment characteristics of rhenium in this type of deposit, with little attention paid to rhenium in other types of deposits. This study reports the occurrence state and enrichment mechanism of rhenium in the Qianjiadian sandstone-type uranium deposit in the Songliao Basin, Northeast China. Sequential extraction revealed that the average proportions of different forms of rhenium are as follows: water-soluble (57.86%) > organic-sulfide-bound (13.11%) > residual (12.26%) > Fe/Mn oxide-bound (10.67%) > carbonate-bound (6.10%). Combining mineralogical analysis techniques such as SEM-EDS, EMPA, and XRD, it has been established that rhenium does not occur as a substitute in sulfides (e.g., molybdenite) or uranium minerals in various types of deposits. Instead, it is mainly adsorbed onto clay minerals and Fe-Ti oxides, and in a small number of other minerals (pyrite, organic matter, and pitchblende). Rhenium is similar to redox-sensitive elements such as uranium and vanadium, and it is transported in a water-soluble form by oxidizing groundwater to the redox transition zone for enrichment. However, unlike uranium, which generally forms as uranium minerals, rhenium is mainly adsorbed and enriched onto clay minerals (kaolinite and interlayered illite–smectite). Most of the rhenium in sandstone-type uranium deposits occurs in an ion-adsorption state, and is easily leached and extracted during in-situ leaching mining of uranium ores. This type of deposit demonstrates excellent production potential and will become a crucial recoverable resource for future rhenium supply. Full article

The Hailijin (HLJ) sandstone-type uranium deposit was newly discovered in the southwestern Songliao Basin in recent years. Different from the roll-front orebody of the sandstone-type uranium deposits with (phreatic oxidation) interlayer redox origin (or phreatic oxidation), the orebody of the HLJ uranium deposit is tabular-shaped and multi-stratiform. The kaolinite content in ore-controlling gray sandstones is significantly higher than that in oxidized sandstones, which have the highest kaolinite content in the less oxidized zone of sandstone-type uranium deposits in the basins of western China (such as Yili Basin and Turpan-Hami Basin). In order to identify the properties of ore-forming fluids and the genesis of the tabular-shaped orebody of the HLJ uranium deposit, trace element, scanning electron microscopy (SEM), X-ray diffraction (XRD), and uranium mineral electron probe (EPMA) analyses of different geochemical zone sandstones in ore-bearing strata were carried out. As a result, kaolinite, illite, and illite/smectite formation (I/S) appear to alternate with one another in ore-controlling gray sandstones, and the content of kaolinite is the highest in ores. SEM analysis also suggests that uranium minerals are commonly adsorbed on the surface of foliated and vermicular kaolinite or trapped within micropores of kaolinite. In this case, it is inferred that kaolinite in ore-controlling gray sandstones is of epigenetic origin, and the ore-bearing sandstones have undergone at least one transformation of acidic fluids. Combined with the regional paleoclimate, regional tectonics, and regional burial history, it is concluded that the acidic fluid originated from the uranium-rich source rocks of the Lower Cretaceous Jiufotang Formation, and the tabular-shaped orebody of the HLJ uranium deposit was formed by exudative metallogeny. When the uranium-rich acidic organic fluids exuded upward from deep levels along the faults to the target strata, the solubility of uranium and other polymetallic elements decreased because of the decrease in temperature and pressure, and uranium eventually precipitated and accumulated in sandstones with suitable permeability and porosity. However, it cannot be ruled out that the superimposition and transformation of uranium mineralization was caused by phreatic oxidation or local interlayer redox during the interval of exudative metallogeny. Full article

The solubility of lanthanum in indium and Ga–In alloys containing 21.8, 40 and 70 wt. % In was determined experimentally at temperatures up to 1081 K. The low temperature limit depended on the melting point of the alloy. The solubility was measured using isothermal saturation and high-temperature filtration methods. The phase composition of solid intermetallic compounds formed in the ternary La–Ga–In systems of various compositions was determined by X-ray diffraction. Activity coefficients of lanthanum in the alloys based on gallium, indium and three Ga–In mixtures (21.8, 40 and 70 wt. % In) were calculated. Temperature dependencies of thermodynamically possible separation factors for the uranium/lanthanum couple in “LiCl–KCl–CsCl melt–liquid alloy” systems were derived for various gallium–indium alloys. Full article

The complex contamination of groundwater near radioactive waste repositories by nitrates and actinides is a common problem for many nuclear fuel cycle facilities. One of the effective methods to remove nitrates and reduce actinide migration activity is bioremediation through the activation of native microbial communities by soluble electron donors and carbon sources. This work evaluated the effectiveness of using simple and complex electron donors to remove nitrate in the microbial community in an aquifer near the B2 storage of the Siberian Chemical Combine (Seversk, Siberia). The addition of sugar and milk whey led to the maximum efficiency of nitrate-ion removal and a decrease in the redox potential of the system, creating optimal conditions for the immobilization of actinide. Special attention was paid to the behavior of uranium, plutonium, neptunium, and americium under conditions simulating groundwater when sugar, acetate, and milk whey were added and when microbial metabolic products were formed. Neither microbial metabolites nor organic solutions were found to have a significant effect on the leaching of neptunium. At the same time, for plutonium, a decrease in yield was observed when rocks were treated with organic solutions were compared to groundwater treatment without them. Plutonium leaching is significantly affected by rock composition. In rocks with a low clay fraction content, its yield can reach 40%. At the same time, microbial metabolites can increase americium (Am) desorption from rocks with a low clay fraction content. Additionally, particle size analysis was performed using a step-by-step filtration approach, aiming to evaluate the risks that are associated with colloidal phase formation. It was shown that microbiological stimulation resulted in particle enlargement, substantially diminishing the presence of actinides in the form of dissolved or sub-50 nm nanoparticles. This outcome significantly reduced the potential for colloidal and pseudocolloidal transfer, thereby lowering associated risks. Full article

The solubility of uranium (U) in hydrothermal fluid is thought to be controlled by oxidation. In general, uranium is mainly transported as U(VI) in oxidized fluid, but precipitated as U(IV) in reduced fluid. However, many geological observations indicate that metamorphic fluids, which are buffered by metamorphic rocks with oxidized protoliths such as oxidized pelite or altered marine basalt, are not enriched in U. To explore the reason of the low solubility of U in metamorphic fluids, we simulated the hydrous speciation and solubility of U in fluids that are in equilibrium with rocks. The simulations were conducted at pressure–temperature (P-T) conditions of greenschist and amphibolite facies metamorphism. The results show that U is mainly dissolved as U(IV), instead of U(VI), in metamorphic fluids. The solubility of U remains at a low level of ~10⁻¹² molal, and is not significantly influenced by metamorphic temperature, pressure, and fluid salinity. This result is consistent with geological observations and, thus, can explain the low-U nature of natural metamorphic fluids. The simulation also shows high solubility of U(VI) (1.3 × 10⁻⁷ molal) in oxidized pelite-buffered fluids at low temperature (<250 °C), consistent with the geological fact that U can be mobilized by low-temperature geofluids. Full article

Evaluation of the mobility behaviour of radionuclides under highly saline and alkaline conditions is a major concern for the performance assessment of radioactive waste disposal. The aim of this study was to determine the effect of up to 2.8 mol/kg_solution content of NaNO₃, on the solubility and the retention of U(VI) at 22 °C onto a hardened cement paste (HCP) prepared from ordinary Portland cement (CEM I). To avoid the interference of the high salt concentration and ionic strength, and because of the expected low solubility of uranium under such alkaline conditions, time-resolved laser fluorescence spectroscopy (TRLFS) was selected to accurately measure U(VI) concentration in solution using the standard addition method in 85% H₃PO₄. This allows both limiting the dilution and matrix effects and determining the resulting [U(VI)] in solution with acceptable precision for the distribution factor (R_d) in both sorption and desorption experiments. The operational solubility limit measured at high ionic strength lowered by a factor of three compared to the reference cementitious condition, and its R_d values decreased by a factor ca. four. The sorption of U(VI) appears to be reversible under these conditions. Full article

Uranyl sulphate minerals are common alteration phases in uranium mines and uraniferous waste deposits where they occur in conjunction with other products of acidic drainage such as jarosite. Although not persistent in nature due to their high solubility, they may play an important role in governing uranium mobility during the operational and immediate post-closure environment of an engineered radioactive waste repository where oxidising conditions prevail. One such mineral, johannite (Cu(UO₂)₂(SO₄)₂(OH)₂·8H₂O), is of particular interest given the stated intention of several countries to use copper canisters in the disposal of spent nuclear fuel. A museum reference sample of johannite has been characterised by luminescence and multiple-laser Raman spectroscopy, resulting in the first reported luminescence excitation and emission spectra for this mineral. Well-defined Raman features were observed using 785, 633, and 532 nm lasers with the resolved peaks corresponding well to the published spectra. The Raman spectrum measured with the 457 nm laser was mostly masked by a series of repeating doublets attributed to the luminescence emission features, from which band spacing values of 831 and 823 cm⁻¹ were extracted; the former corresponded to both the resolved 785 nm ν₁(UO₂)²⁺ peak position and the band spacing value obtained from the first reported luminescence emission spectrum for johannite. Four emission and nine excitation peaks were resolved from the luminescence spectra. The findings indicate that a suite of complementary laser-based techniques offer the potential for real-time characterisation of johannite formed in environments where intrusive sampling, transportation, and ‘off-site’ laboratory analysis are not feasible. Full article

Due to the high solubility of uranyl sulfate and selenite minerals, the investigation involving the determination of the crystal structures and physical properties of these minerals is essential in actinide environmental chemistry for the simulation of uranium migration from uraninite deposits and nuclear waste repositories. However, the determination of the complete crystal structures of the uranyl sulfate minerals johannite $(\mathrm{Cu}\left({\mathrm{UO}}_2{)}_2{\left({\mathrm{SO}}_4\right)}_2{\left(\mathrm{OH}\right)}_2·8{\mathrm{H}}_2\mathrm{O}\right)$ and pseudojohannite $({\mathrm{Cu}}_3\left({\mathrm{UO}}_2{)}_4{\left({\mathrm{SO}}_4\right)}_2{\mathrm{O}}_4{\left(\mathrm{OH}\right)}_2·12{\mathrm{H}}_2\mathrm{O}\right)$ and the uranyl selenite mineral derriksite (${\mathrm{Cu}}_4[(\left({\mathrm{UO}}_2\right){({\mathrm{SeO}}_3)}_2{\left(\mathrm{OH}\right)}_6]$) has not been feasible so far. In this work, the crystal structures of these minerals, including the positions of the hydrogen atoms, are determined using first principles solid-state methods based on periodic density functional theory using plane wave basis sets and pseudopotentials. The lattice parameters and associated geometrical variables as well as the corresponding X-ray diffraction patterns derived from the computed crystal structures are in excellent agreement with their experimental counterparts, derived from the corresponding experimental structures lacking the hydrogen atom positions. The complete crystal structure of derriksite is also determined by refinement from X-ray diffraction data, the resulting structure being consistent with the computed one. The knowledge of the positions of H atoms is of fundamental importance not only because they define the corresponding hydrogen bond networks holding together the atoms in the structures, but also because it allows for the efficient, inexpensive and safe determination of the physical properties using first principles methods. This feature is particularly important in the case of uranium-containing minerals due to their radiotoxicity, complicating the handling of the samples and experimental measurements. In this work, from the computed crystal structures, the elasticity tensors of these minerals are computed using the finite displacement method and a rich set of elastic properties including the bulk, Young’s and shear moduli, the Poisson’s ratio, ductility, anisotropy and hardness indices and bulk modulus derivatives with respect to pressure derivatives are determined. Full article

Uranium and arsenic are two pollutants commonly found in groundwater near uranium mines. However, the reactivity of U(VI) and As(V) need to be carefully investigated to better understand their fate and transport in the environment. In this study, the reactivity of U(VI) and As(V) were studied under various pH, bicarbonate, and Ca²⁺ levels. In air-equilibrated systems, the reactivity of U(VI) and As(V) generally decreased with the increase in pH, as evidenced by the solubility of U(VI) and As(V) increasing along with the elevation of pH. At pH = 8, 44.70% and 37.81% of initially added U(VI) and As(V) remained soluble. The addition of 1 mM of bicarbonate increased the reactivity of U(VI) and As(V) at mild acidic to neutral pH; however, the presence of bicarbonate significantly increased the solubility of U(VI) at mild alkaline condition, as nearly all U(VI) remained soluble at pH values of 8 and 9. After the addition of Ca²⁺, the solubility of both U(VI) and As(V) decreased at mild acidic to neutral pH ranges; however, the addition of Ca²⁺ markedly increased the soluble percentages of U(VI) at neutral pH, in which the condition 97.81 ± 2.95% of U(VI) remained soluble. Comparatively, only 36.13 ± 4.98% and 1.69 ± 1.08% of U(VI) were soluble at the same pH in air-equilibrated and bicarbonate systems. Our study demonstrated that U(VI) and As(V) are less reactive at neutral to alkaline conditions. Furthermore, the addition of bicarbonate and Ca²⁺ can further reduce the reactivity of U(VI) and As(V) at neutral to alkaline conditions. The findings of this study contribute to a deeper understanding of the fate and transport of U(VI) and As(V) in groundwater and could aid in better designing of U(VI) and As(V) removal processes. Full article

We explored two approaches to recover uranium and plutonium from aqueous solutions at pH 4 and pH 7 using water-soluble star-like polyacrylamide polymers with a dextran core. In the first approach, a solution comprising a neutral or ionomer polymer was mixed with a radionuclide solution to form polymer–metal complexes that were then retained by ultrafiltration (UF) membranes under applied pressure. The same polymers were first deposited on the membrane in the second approach using pressure-driven flow. The applied polymers had an overall diameter of gyration of 120 nm, which exceeded the nominal diameter of the UF membrane pores. The polymers showed a high affinity to uranyl but could also be used to extract Pu from neutral or near-neutral pH solutions. Direct-flow single-step filtration and alpha spectrometry demonstrated that the UF membranes containing star-like copolymers could recover 99% of U and up to 60% of Pu from deionized water after filtering 15 mL solutions containing 25 ppm and 33 ppb of the actinides, correspondingly. The sorption capacity of the polymers for uranium could be measured as 1mg U per mg of the polymer after six subsequent filtration steps. Alpha spectroscopy of the deposited actinides revealed peculiarities of the structural organization of polymers and their complexes with U or Pu, depending on the approach. Though both approaches were efficient, the second approach (deposition of the polymer on the membrane followed by filtration) has an additional advantage of protecting the membrane pores from capillary collapse by filling them with the polymer chains. Therefore, these polymer-modified membranes could be used either in continuous or multi-step filtration process with drying after each step without deterioration of their sorption characteristics. Full article

In order to realize sustainable development, it is beneficial to explore an appropriate process to recover the radionuclides contained in tantalum-niobium slag. By micro-mineralogical analysis and roasting experiments, the effect of uranium-thorium leaching from a refractory tantalum-niobium slag is investigated. The uranium and thorium content in the slag is 2.26 × 10³ mg/kg and 7.84 × 10³ mg/kg, which have large recovery value. As the surface area and pore size of the slag are very small, the leaching agent cannot fully penetrate the particles. Various methods of characterization are used to analyze the mineralogical properties of roasted slag at different temperatures. The leaching ratio of U-Th is 90.84% and 96.62% at the optimum roasting temperature of 500 °C, which are about 39% and 27% higher than original samples. The oxidants Fe³⁺, O₂ and Mn can also promote the conversion of insoluble U(IV) to soluble U(VI). Roasting reduces the content of organic C and S, thereby preventing reduction of U(VI), and increasing pore size as well as specific surface area also promote radionuclide leaching. Thus, the roasting method at 500 °C can destroy the surface wrapping structure of radionuclides, reduce the internal density of minerals, and improve uranium-thorium leaching ratio significantly. It is of great practical significance to reduce the radioactive hazard of waste tantalum-niobium slag and to strengthen the sustainable utilization of resources by suitable process improvement techniques. Full article