Uranyl Phosphate Research Articles

Unexpected enhancement effects of phosphate on co-immobilization of uranyl arsenate under acidic conditions

Understanding the formation of uranyl-arsenate compounds (M(UO2)2(AsO4)2·nH2O, M represents divalent metallic cations) is of great importance in controlling the mobility and fate of uranium (U) and arsenic (As) in the natural environment. Phosphate is a ubiquitous coexisting ion with properties similar to arsenate and can complex with uranyl to form uranyl phosphate compounds, thus potentially affecting the formation of uranyl-arsenate compounds. Herein, the effect of phosphate, on the immobilization of uranyl, arsenate and divalent metallic cations (e.g., Fe2+, Mg2+, Ni2+, Cu2+) was explored. Surprisingly, the presence of phosphate promoted the immobilization of uranyl arsenate with the divalent metallic cations under acidic conditions. For example, at pH 3.0, the immobilization efficiency of uranyl and arsenate in the uranyl-arsenate-Fe2+ system increased from 20.6 % and 18.6 % to 82.6 % and 52.2 %, respectively. Moreover, the chemical stability of the formed uranyl arsenate-bearing compounds in the presence of phosphate is significantly improved, and the TCLP leachability of As and U decreased by 81 % and 97 %, respectively. The experimental results illustrated that with PO43- served as a proton acceptor, uranyl and arsenate species were changed and more metallic cations participate in immobilization. Gibbs free energy and Gibbs free energies change also illustrated that the formation of Fe(UO2)2(AsO4)2·5H2O was relatively thermodynamically favorable in the presence of phosphate. The results of thermodynamic calculations could account for the enhancement effects of phosphate on immobilization of uranyl arsenate. The findings have important implications for the mobility and fate of U and As and the solution of their co-contamination, especially in acidic environments.

The effect of bacteria on uranium sequestration stability by different forms of phosphorus

ABSTRACT Immobilisation of uranium (U (VI)) by direct precipitation of uranyl phosphate (U-P) exhibits a great potential application in the remediation of U (VI)-contaminated environments. However, phosphorus, vital element of bacteria’s decomposition, absorption and transformationmay affect the stability of U (VI) with ageing time. The main purpose of this work is to study the effect of bacteria on uranium sequestration mechanism and stability by different forms of phosphorus in a water sedimentary system. The results showed that phosphate effectively enhanced the removal of U (VI), with 99.84%. X-Ray Diffraction (XRD), Scanning Electron Microscopy and Energy Dispersive Spectrometer (SEM-EDS), and X-ray Photoelectron Spectroscopy (XPS) analyses imply that U (VI) and U (IV) co-exist on the surface of the samples. Combined with BCR results, it demonstrated that bacteria and phosphorus have a synergistic effect on the removal of U (VI), realising the immobilisation of U (VI) from a transferable phase to a stable phase. However, from a long-term perspective, the redissolution and release of uranium immobilisation of U (VI) by pure bacteria with ageing time are worthy of attention, especially in uranium mining environments rich in sensitive substances. This observation implies that the stability of the uranium may be impacted by the prevailing environmental conditions. The novel findings could provide theoretical evidence for U (VI) bio-immobilisation in U (VI)-contaminated environments.

Uranium enrichment driven by paleomarine condition and event deposition: Insights from the lower Cambrian Niutitang Formation organic-rich shales in northeastern Guizhou, South China

Organic-rich shale related uranium (U) mineralization has attracted widespread attention as a strategic and clean alternative to fossil energy and a paleoceanic redox proxy. A comprehensive study of mineralogy, organic geochemistry and elemental geochemistry of the lower Cambrian Niutitang Formation organic-rich shales in northeastern Guizhou, South China was conducted to address this issue. SEM-EDS results showed that the U occurrence state in the Niutitang Formation shales is dominated by nanoscale U minerals, mainly including coffinite, brannerite, U-bearing apatite and U-bearing xenotime. Various states of U are closely associated with organic matter, apatite, pyrite and clay minerals. Based on geochemical indexes, paleomarine condition and event deposition jointly drove the U enrichment in the Niutitang shales, in which hydrothermal activities and/or volcanic eruptions increased U fluxes in seawater and euxinic environment with high primary productivity provided a favorable condition for U reduction. The adsorption, complexation and reduction of UO22+ by organic matter and the formation of uranyl phosphate complexes by the combination of phosphate and UO22+ accelerated U immobilization and enrichment from bottom water to sediments. The microbial activities (e.g., BSR) in this process created favorable euxinic conditions and released inorganic-phase P to provide available ligands for UO22+. The U enrichment models of the lower Cambrian Niutitang shales in northeastern Guizhou were established. This paper provides a new insight into the U enrichment mechanism in organic-rich shales, and may also have implications for the applicability of U as redox proxy and the exploration of organic-rich shale related U deposits.

Immobilization of hexavalent uranium U(VI) by hydroxyapatite under oxic conditions

The immobilization of hexavalent uranium U(VI) by hydroxyapatite (HAP) was investigated under oxic conditions as a function of pH and surface loading ([U(VI)]0/[HAP]0) to evaluate the applicability of HAP as migration barriers or waste forms in nuclear waste repositories. This study focused on the retention mechanisms, which were sought by integrating the solid-phase characterization (e.g., X-ray diffraction, scanning electron microscopy with energy dispersive spectroscopy, and U LIII-edge X-ray absorption spectroscopy) with the solution-phase analysis of dissolved Ca, P, and U. At acidic pH, due to the increasing solubility of HAP, U(VI) retention is mainly controlled by the formation of a uranyl phosphate following HAP dissolution. Importantly, this phosphate is in the form of a solid solution with Na meta-autunite being the principal component, which considerably expands the stable domain of uranyl phosphates compared to the pure phases (e.g., chernikovite, Na meta-autunite, and meta-autunite). At neutral to basic pH, however, the uranyl phosphate formation does not prevail till [U(VI)]0/[HAP]0 = 25 mg/g, below which the formation of U(VI)-phosphate ternary surface complexes mainly accounts for U(VI) retention. At basic pH, the surface substitution of PO43− for CO32− and the dominance of uranyl carbonate species make surface complexation less favorable under this pH condition. In this study, the initially present U(VI) is near completely immobilized (> 99.99 %) by HAP, with the greatest retention noted at circumneutral pH, thus demonstrating the effectiveness of HAP for the containment of U(VI) under ambient geochemical conditions.

Phosphate and illite colloid pose a synergistic risk of enhanced uranium transport in groundwater: A challenge for phosphate immobilization remediation of uranium contaminated environmental water

The phosphorus-containing reagents have been proposed to remediate the uranium contaminated sites due to the formation of insoluble uranyl phosphate mineralization products. However, the colloids, including both pseudo and intrinsic uranium colloids, could disturb the environmental fate of uranium due to its nonnegligible mobility. In this work, the transport pattern and micro-mechanism of uranium coupled to phosphate and illite colloid (IC) were investigated by combining column experiments and micro-spectroscopic evidences. Results showed that uranium transport was facilitated in granular media by forming the intrinsic uranyl phosphate colloid (such as Na-autunite) when the pH > 3.5 and CNa+ < 10 mM. Meanwhile, the mobility of uranium depended greatly on the typical water chemistry parameters governing the aggregation and deposit of intrinsic uranium colloids. However, the attachment of phosphate on illite granule increased the repulsive force and enhanced the dispersion stability of IC in the IC-U(VI)-phosphate ternary system. The non-preequilibrium transport and retention profiles, HRTEM-mapping, as well as TRLFS spectra revealed that the IC enhanced uranium mobility by forming the ternary IC-uranyl phosphate hybrid, and acted as the coagulation preventing agent for uranyl phosphate particles. This observed facilitation of uranium transport resulted from the formation of intrinsic uranyl phosphate colloids and IC-uranyl phosphate hybrids should be taken into consideration when evaluating the potential risk of uranium migration and optimizing the in-situ mineralization remediation strategy for uranium contaminated environmental water.

Efficient removal of uranium from acidic mining wastewater using magnetic phosphate composites

Uranium mining operations produce large volumes of acidic uranium mining wastewater, necessitating the development of environmentally friendly and recyclable materials for efficient uranium removal and recovery. The current study successfully produced hydroxyapatite (HAP-L) and magnetic phosphate composites (CaFeP-1, CaFeP-2, and FePO4) through a combination of mixing, ultrasonication, hydrothermal precipitation, and calcination methods. The research explores the influence of various parameters such as pH, solid–liquid ratio, contact time, initial uranium concentration, co-existing ions, and recyclability on the uranium removal efficiency of these materials. The findings indicate exceptional uranium adsorption capacities, with CaFeP-1 exhibiting the highest capacity among the materials, especially in acidic environments. Moreover, CaFeP-1 displays strong resistance to interference from other ions and can be recycled multiple times while maintaining high removal rates. Treatment of acidic uranium mining wastewater by CaFeP-1 results in pH adjustment and the reduction of uranium and other ion concentrations, making it a promising solution for comprehensive remediation of acidic uranium mining wastewater. The U(VI) removal mechanism by CaFeP-1 was validated through XRD, FT-IR, and XPS results. The U(VI) removal was attributed to processes such as dissolution-precipitation, surface complexation, and ion exchange. The formation of sodium uranyl phosphate hydrate was identified as a new product following U(VI) abatement by CaFeP-1. In summary, CaFeP-1 shows great potential for the effective treatment of acidic uranium mining wastewater.

Uranium biomineralization by immobilized Chryseobacterium sp. strain PMSZPI cells for efficient uranium removal

Uranium (U) contamination is hazardous to human health and the environment owing to its radiotoxicity and chemical toxicity and needs immediate attention. In this study, the immobilized biomass of Chryseobacterium sp. strain PMSZPI isolated from U enriched site, was investigated for U(VI) biomineralization in batch and column set-up. Under batch mode, the fresh or lyophilized cells successfully entrapped in calcium alginate beads demonstrated effectual U precipitation under acid and alkaline conditions. The maximum removal was detected at pH 7 wherein ∼98–99% of uranium was precipitated from 1 mM uranyl carbonate solution loading ∼350 mg U/g of biomass within 24 h in the presence of organic phosphate substrate. The resulting uranyl phosphate precipitates within immobilized biomass loaded beads were observed by SEM-EDX and TEM while the formation of U biomineral was confirmed by FTIR and XRD. Retention of phosphatase activity without any loss of uranium precipitation ability was observed for alginate beads with lyophilized biomass stored for 90 d at 4 °C. Continuous flow through experiment with PMSZPI biomass immobilized in polyacrylamide gel exhibited U loading of 0.8 g U/g of biomass at pH 7 using 1 l of 1 mM uranyl solution. This investigation established the feasibility for the application of immobilized PMSZPI biomass for field studies. Environmental implicationUranium contamination is currently a serious environmental concern owing to anthropogenic activities and needs immediate attention. We have developed here a biotechnological method for successful uranium removal using immobilized cells of a uranium tolerant environmental bacterium, Chryseobacterium sp. strain PMSZPI isolated from U ore deposit via phosphatase enzyme mediated uranium precipitation. The ability of immobilized PMSZPI cells to precipitate U(VI) as long-term stable U phosphates under environmental conditions relevant for contaminated waters containing high concentrations of U that exerts toxicity for biological systems is explored here. The long term stability of the immobilized biomass without compromising its U removal capacity shows the relevance of the bioremediation strategy for uranium contamination proposed in this work.

Incorporation of U(IV) in monazite-cheralite ceramics under oxidizing and inert atmospheres.

This work is the first attempt to prepare Nd1-xCaxUxPO4 monazite-cheralite with 0 < x ≤ 0.1 by a wet chemistry method. This method relies on the precipitation under hydrothermal conditions (T = 110 °C for four days) of the Nd1-xCaxUxPO4·nH2O rhabdophane precursor, followed by its thermal conversion for 6 h at 1100 °C in air or Ar atmosphere. The optimized synthesis protocol led to the incorporation of U and Ca in the rhabdophane structure. After heating at 1100 °C for 6 h in air, single-phase monazite-cheralite samples were obtained. However, α-UP2O7 was identified as a secondary minor phase in the samples heated under Ar atmosphere. The U speciation in the samples converted in an oxidising atmosphere was carefully characterized using synchrotron radiation by combining HERFD-XANES and XRD. These results showed the presence of a minor secondary phase containing hexavalent uranium and phosphate with a stoichiometry of U : P = 0.78. This highly labile uranyl phosphate phase incorporated 21 mol% of the uranium initially precipitated with the rhabdophane precursor. This phase was completely removed by a washing protocol. Thus, single-phase monazite-cheralite was obtained through the wet chemistry route described in this work with a maximum U loading of x = 0.08.

Speciation studies at the Illite - solution interface: Part 2 – Co-sorption of uranyl and phosphate ions

Although it is well known that clays and phosphate ions (hereafter referred to as “P”) can contribute to the long term uptake of uranium (U) in a variety of geochemical systems, work is still needed to document the surface speciation of U(VI) and P sorbed on relevant clay minerals such as illite. Following on from previous work showing strong sorption of phosphate ligands on the surface of a homoionic Na-illite ([1]), we addressed the (competitive/synergistic) mechanisms of (co)sorption of trace levels of uranyl ions (1–10 µM) and phosphate ligands (100 µM) onto this clay, and the identity of the surface species formed, by in situ spectroscopy monitoring of the clay-solution interface along sorption. We also performed complementary batch sorption experiments and electrophoretic mobility (EM) measurements. Macroscopic data indicated a uranyl sorption dependent on pH, aqueous U concentration and clay-to-solution ratio, a signature of P on the U sorption, and a promotion of P sorption with U concentration. Macroscopic and EM data also suggested mostly reversible mechanisms of P and U co-sorption that confer negative charges on the mineral surface and involve several types of uranyl phosphate surface species and/or surface sites present on the clay edges. FTIR interface spectra confirmed that several types of inner sphere uranyl phosphate surface species formed at acidic pH at the illite-solution interface, as a function of U surface coverage and/or reaction time. An inner-sphere uranyl phosphate surface complex, likely with a U-bridging structure, was formed rapidly on high-affinity surface sites existing in limited quantities on the clay edges. Another U-P surface complex (with a possible P-bridging structure) was progressively formed in increasing amounts with U surface coverage and time on low affinity clay edge sites. Finally, a third U-P surface species having an autunite-like structure (probably a U-P polynuclear surface species) was formed on the illite surface at high U concentration (10 µM). The two later species competed with the existence on the illite surface of inner sphere surface complexes and outer-sphere surface complex of phosphate, which were identified in the absence of U. Information on uranyl surface speciation in the presence of phosphate ligands presented here is novel and provides for the first time in situ spectroscopic evidence of synergistic U-P sorption process leading in the formation of several types of uranyl phosphate sorption species on the surface of illite. These results provide a sound basis for better understanding / prediction of U sorption in the environment, including in clayey formations being considered as long term barriers to radionuclide migration in far field of high level radioactive waste repository.

Microbial adaptations and biogeochemical cycling of uranium in polymetallic tailings

Microorganisms inhabiting uranium (U)-rich environments have specific physiological and biochemical coping mechanisms to deal with U toxicity, and thereby play a crucial role in the U biogeochemical cycling as well as associated heavy metals. We investigated the diversity and functional capabilities of indigenous bacterial communities inhabiting historic U- and Rare-Earth-Elements-rich polymetallic tailings from the Mount Painter Inlier, Northern Flinders Ranges, South Australia. Bacterial diversity profiling identified Actinobacteria as the predominant phylum in all samples. GeoChip analyses revealed the presence of diverse functional genes associated with biogenic element cycling, metal homeostasis/resistance, stress response, and secondary metabolism. The high abundance of metal-resistance and stress-tolerance genes indicates the adaptation of bacterial communities to the “harsh” environmental (metal-rich and semi-arid) conditions of the Northern Flinders Ranges. Additionally, a viable bacterial consortium was enriched from polymetallic tailings. Laboratory experiments demonstrated that the consortium scrubbed uranyl from solution by precipitating a uranyl phosphate biomineral (chernikovite), thus contributing to U biogeochemical cycling. These specialised microbial communities reflect the high specificity of the mineralogy/geochemistry, and biogeography of these U-rich settings. This study provides the fundamental knowledge to develop future applications in securing long-term stability of polymetallic mine waste, and for reprocessing this “waste” to further extract critical minerals.

Recovery of uranium from conversion production sludge by leaching with nitric acid and subsequent ion-exchange concentration

Physicochemical studies of the sludge of uranium conversion production were carried out to determine the possibility of its processing and return of uranium to the nuclear fuel cycle. It has been established that the sludge was mainly represented by calcium compounds: CaSO4·2H2O (60.1 wt%), CaCO3 (25.1 wt%), CaF2 (13.7 wt%), and silicon dioxide (1.2 wt%). The content of uranium in the sludge was 0.15 wt%. It was shown that it was possible to achieve high degrees of uranium extraction from the sludge using nitric acid as a leaching agent. The use of phosphorus-containing ion-exchanger Tulsion CH93 ensured the effective concentration of uranium from highly acidic pregnant leach solutions. The full dynamic exchange capacity achieved 15.7 kg m−3. The degree of uranium desorption by ACBM (ammonium carbonate/bicarbonate mixture) solutions was 83%. The final product was ammonium uranyl phosphate hydrate NH4UO2PO4∙3H2O with a uranium content of 52.5 wt%.

Synergistic effects of hydrogen peroxide and phosphate on uranium(VI) immobilization: implications for the remediation of groundwater at decommissioned in situ leaching uranium mine.

The processes of acid in situ leaching (ISL) uranium (U) mines cause the pollution of groundwater. Phosphate (PO43-) has the potential to immobilize U in groundwater through forming highly insoluble phosphate minerals, but the performance is highly restricted by low pH and high sulfate concentration. In this study, hydrogen peroxide (H2O2) and PO43- were synergistically used for immobilizing U based on the specific properties of groundwater from a decommissioned acid ISL U mine. The removal mechanisms of U and the stability of U on the formed minerals were elucidated by employing X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy and kinetic experiments. Our results indicated that the removal of U by simultaneously adding H2O2 and PO43- was significantly higher than the removal of U by individually adding H2O2 or PO43-. The removal of U increased with increasing PO43- concentration from 20 to 200 mg L-1 while decreased with increasing H2O2 concentration from 0.003 to 0.3%. Specifically, the removal efficiency of U from groundwater reached 98% after the application of 0.003% H2O2 and 200 mg L-1 PO43-. Amorphous iron phosphate that preferentially formed at low H2O2 and high PO43- concentrations played a dominant role in U removal, while the formations of schwertmannite and crystalline iron phosphates may be also contributed to the removal of U. This was significantly different from the immobilization mechanism of U through the formation of uranyl phosphate minerals after adding phosphate. The kinetic experimental results suggested that the immobilized U had a good stability. Our research may provide a promising method for in situ remediating U-contaminated groundwater at the decommissioned acid ISL U mines.

Uranium bioprecipitation mediated by a phosphate-solubilizing Enterobacter sp. N1-10 and remediation of uranium-contaminated soil

Uranium (U) pollution in soils is prevalent worldwide and poses a significant health risk that will require remediation approaches. However, traditional U bioreduction by sulfate reducing bacteria (SRB) are sensitive to oxygen and are not suitable for treating aerobic topsoil. Bioprecipitation of U into uranyl phosphate (UP) mediated by phosphate-solubilizing microorganism (PSM) is not affected by oxygen. In this study, PSM strains were isolated and used for U-contaminated soil remediation. Microbial metabolites and the mechanism of PSM bioprecipitation were revealed. The results showed that strain Enterobacter sp. N1-10 had the highest phosphate-solubilizing capacity (dissolved P was 409.51 ± 8.48 mg/L). Uranium bioprecipitation was investigated by culturing the bacterium in the presence of 50 mg/L U and in the cell-free culture supernatant. The results showed that strain N1–10 had a high U removal rate (99.45 ± 0.43 %) after adding 50 mg/L U to the culture medium. A yellow precipitate was immediately formed when uranyl nitrate solution was added to the cell-free culture supernatant. The analysis indicated that bacterium produced lactic acid (37.58 mg/L), citric acid (4.76 mg/L), succinic acid (2.03 mg/L), and D-glucuronic acid (1.94 mg/L); the four organic acids solubilized Ca3(PO4)2 to form stable uranyl phosphate precipitate. The application of strain N1-10 and Ca3(PO4)2 significantly decreased the bioavailability of soil U (43.54 ± 0.52 %). In addition, pot experiments showed that PSM N1-10 and Ca3(PO4)2 promoted plant growth and markedly reduced U accumulation by pakchoi. These results demonstrate that PSM N1-10 and Ca3(PO4)2 exhibit a great potential for U bioremediation.

Kinetics of Na- and K- uranyl arsenate dissolution

We integrated aqueous chemistry analyses with geochemical modeling to determine the kinetics of the dissolution of Na and K uranyl arsenate solids (UAs(s)) at acidic pH. Improving our understanding of how UAs(s) dissolve is essential to predict transport of U and As, such as in acid mine drainage. At pH 2, Na0.48H0.52(UO2)(AsO4)(H2O)2.5(s) (NaUAs(s)) and K0.9H0.1(UO2)(AsO4)(H2O)2.5(s) (KUAs(s)) both dissolve with a rate constant of 3.2 × 10−7 mol m−2 s−1, which is faster than analogous uranyl phosphate solids. At pH 3, NaUAs(s) (6.3 × 10−8 mol m−2 s−1) and KUAs(s) (2.0 × 10−8 mol m−2 s−1) have smaller rate constants. Steady-state aqueous concentrations of U and As are similarly reached within the first several hours of reaction progress. This study provides dissolution rate constants for UAs(s), which may be integrated into reactive transport models for risk assessment and remediation of U and As contaminated waters.

Structure, Stability, and Acidity of the Uranyl Arsenate Dimer in Aqueous Solution.

The migration of uranium (U) in the surficial environment has received considerable attention. Due to their high natural abundance and low solubility, autunite-group minerals play a key role in controlling the mobility of U. However, the formation mechanism for these minerals has yet to be understood. In this work, we took the uranyl arsenate dimer ([UO2(HAsO4)(H2AsO4)(H2O)]22-) as a model molecule and carried out a series of first-principles molecular dynamics (FPMD) simulations to explore the early stage of the formation of trögerite (UO2HAsO4·4H2O), a representative autunite-group mineral. By using the potential-of-mean-force (PMF) method and vertical energy gap method, the dissociation free energies and the acidity constants (pKa's) of the dimer were calculated. Our results show that the U in the dimer holds a 4-coordinate structure, which is consistent with the coordination environment observed in trögerite mineralogy, in contrast to the 5-coordinate U in the monomer. Furthermore, the dimerization is thermodynamically favorable in solution. The FPMD results also suggest that tetramerization and even polyreactions would occur at pH > 2, as observed experimentally. Additionally, it is found that trögerite and the dimer have very similar local structural parameters. These findings imply that the dimer could serve as an important link between the U-As complexes in solution and the autunite-type sheet of trögerite. Given the nearly identical physicochemical properties of arsenate and phosphate, our findings suggest that uranyl phosphate minerals with the autunite-type sheet may form in a similar manner. This study therefore fills a critical gap in atomic-scale knowledge of the formation of autunite-group minerals and provides a theoretical basis for regulating uranium mobilization in P/As-bearing tailing water.

The role of uranyl complex decomposition and redox conditions in the precipitation of hydrothermal uranium deposits: Insights from chlorite mineralogy and geochemistry in the Shazhou uranium deposit, Xiangshan, SE China

Uranium precipitation involves the decomposition of uranyl complexes and the reduction of hexavalent uranium, which can occur sequentially or simultaneously within one redox reaction. The redox condition of hydrothermal fluid plays a vital role in controlling the migration and precipitation of uranium in hydrothermal uranium deposits. However, little attention has been paid to the role of uranyl complex decomposition in uranium precipitation. In this study, chlorite mineralogy and geochemistry were examined to clarify the process of uranium precipitation in the Shazhou deposit, Xiangshan uranium orefield, Southeast China. Based on comprehensive petrographic and mineral chemistry studies of chlorites obtained from altered granite porphyries and uranium ores, five types of chlorites were identified: (1) chlorite present in the form of pseudomorphous biotite, which was produced by the hydrothermal alteration of biotite in rocks that underwent hematitization and chloritization (Chl-I); (2) chlorite filling the cleavage cracks in biotite in rocks that underwent hematitization and chloritization (Chl-II); (3) chlorite occurring in pyrite veins (Chl-III); (4) chlorite intergrown with pitchblende in ore veins (Chl-IV); and (5) chlorite occurring in calcite veins (Chl-V). Chlorite geothermometry revealed that the formation temperatures of the five types of chlorites ranged from 219 °C to 254 °C. Mineral chemistry analyses revealed that the five types of chlorites formed in a reductive fluid environment, where the oxygen fugacity at different stages is similar, with log fO2 values ranging from −41.6 to −39.1. Uranium precipitation started only in stage Chl-IV. The examination of the mineral assemblage revealed that the ore-forming fluid was rich in F−, HPO32−, and CO32−. Comprehensive investigation of chemistry and physicochemical conditions of the ore-forming fluid revealed that oxidized uranium (UO22+) could be complexed with HPO42− and F−, and uranyl phosphate and the uranyl fluoride complexes were the main uranium species when uranium precipitation and the decomposition occurred at stage Chl-IV. However, the assessment of oxygen fugacity of the solution equilibria between the UO2(s) and the uranyl phosphate and uranyl fluoride complexes revealed that the reducibility of the fluid favoring the reduction of uranyl ions (UO22+) to U4+ was insufficient to reduce the uranyl phosphate and uranyl fluoride complexes. This indicates that the breakup of uranyl phosphate and the uranyl fluoride complexes to release uranyl ions should occur first at stage Chl-IV, reducing uranyl ions to U4+, and leading to uranium precipitation. Hence, the decomposition of uranyl complexes played an important role in uranium precipitation. With the increase in pH, uranyl phosphate and the uranyl fluoride complexes gradually decomposed and became reducible. Moreover, the decrease in ligand concentration was conducive to the decomposition of uranyl phosphate and the uranyl fluoride complexes. During the formation of the Shazhou deposit, the fluid boiling process induced the loss of volatiles, such as CO2, CH4, HF, and H2S, leading to an increase in pH and decrease in HPO42−, F−, and CO32− concentrations in the fluid. These factors also led to the decomposition of uranyl fluoride and the uranyl phosphate complexes and the precipitation of fluorapatite and calcite. Uranium was then reduced by the action of Fe2+ and S− (pyrite) from a hexavalent to a tetravalent, and finally, uranium was precipitated to form uranium ores.

Vibrational characterization of the various forms of (solvated or unsolvated) mobile proton in the solid state. Advantages, limitations and open questions

A didactic review of (Raman, infrared and neutron) vibrational spectroscopy procedures to study mobile protonic species (H2O, H3O+, H5O2+, “H+”, NH4+, etc.) in solid hydrates, crystals and ceramics is proposed on the basis of paper published since 1970s. Three materials are taken as representative examples: hydrated uranyl phosphate (HUP), oxonium, hydroxonium and ammonium beta- and beta“-aluminas and nominally anhydrous strontium/barium zirconate perovskite. Particular attention is given to the advantages of isotopic substitution and dilution measurements as a function of temperature and partial ion exchange. The vibrational signatures that we consider as being able to serve as references for the different kinds of proton species observed in the proton conductors are presented. We also discuss the signature of protonic species giving no vibrational signature - or whose Raman and infrared signatures are too weak to be clearly detected – that need to be better characterized and understood. The presence of a strong incoherent inelastic neutron scattering background appears characteristic of (mobile) proton conductors.

Solubility and Thermodynamic Investigation of Meta-Autunite Group Uranyl Arsenate Solids with Monovalent Cations Na and K.

We investigated the aqueous solubility and thermodynamic properties of two meta-autunite group uranyl arsenate solids (UAs). The measured solubility products (log Ksp) obtained in dissolution and precipitation experiments at equilibrium pH 2 and 3 for NaUAs and KUAs ranged from -23.50 to -22.96 and -23.87 to -23.38, respectively. The secondary phases (UO2)(H2AsO4)2(H2O)(s) and trögerite, (UO2)3(AsO4)2·12H2O(s), were identified by powder X-ray diffraction in the reacted solids of KUA precipitation experiments (pH 2) and NaUAs dissolution and precipitation experiments (pH 3), respectively. The identification of these secondary phases in reacted solids suggest that H3O+ co-occurring with Na or K in the interlayer region can influence the solubilities of uranyl arsenate solids. The standard-state enthalpy of formation from the elements (ΔHf-el) of NaUAs is -3025 ± 22 kJ mol-1 and for KUAs is -3000 ± 28 kJ mol-1 derived from measurements by drop solution calorimetry, consistent with values reported in other studies for uranyl phosphate solids. This work provides novel thermodynamic information for reactive transport models to interpret and predict the influence of uranyl arsenate solids on soluble concentrations of U and As in contaminated waters affected by mining legacy and other anthropogenic activities.

Lactic acid bacteria induce phosphate recrystallization for the in situ remediation of uranium-contaminated topsoil: Principle and application

Uranium (U) contamination often occurs in the topsoil (arable layer), and is a serious threat to crop growth. However, conventional microbial reduction methods are sensitive to oxygen and cannot be used to treat aerobic topsoils. In this study, phosphate-solubilizing microorganisms (PSM) were isolated from U-contaminated topsoil and used for soil remediation. Microbial metabolites and products were analyzed, and the pathways and mechanisms of PSM immobilization were revealed. The results showed that strain PSM8 had the highest phosphate-solubilizing capacity (dissolved P was 208 ± 5 mg/L) and the highest U removal rate (97.3 ± 0.1%). Multi-technical analyses indicated that bacterial surface functional groups adsorbed (UO2)2+ ions on the cell surface, glycolysis produced 3–10 mg/L of lactic acid (pH 4.7–6.0), and lactic acid solubilized Ca3(PO4)2 to form stable chernikovite (a type of uranyl phosphate) on the cell surface. The coupled application of Ca3(PO4)2 and strain PSM8 significantly reduced the bioavailability of soil U (62 ± 11%), converting U from the exchangeable to the residual phase and P from the steady to the available form. In addition, pot experiments showed that soil remediation promoted crop growth and significantly reduced U uptake and toxicity to photosynthetic systems. These findings demonstrate that PSM and Ca3(PO4)2 are good coupled fertilizers for U-contaminated agricultural soil.

A comprehensive study on the interaction of Eu(III) and U(VI) with plant cells (Daucus carota) in suspension

Daucus carota suspension cells showed a high affinity towards Eu(III) and U(VI) based on a single-step bioassociation process with an equilibrium after 48–72 h. Cells responded with an increased metabolic activity towards heavy metal stress. Luminescence spectroscopy pointed to multiple species for both f-block elements in the culture media, providing initial hints of their interaction with cells and released metabolites. Using nuclear magnetic resonance spectroscopy, we could prove that malate, as an released metabolite in the culture medium, was found to complex with U. Luminescence spectroscopy also showed that Eu(III)-EDTA species are interacting with the cells. Furthermore, Eu(III) and U(VI) coordination is dominated by phosphate groups provided by the cells. We found that Ca ion channels of D. carota cells were involved in the uptake of U(VI), which led to a bioprecipitation of U(VI) in the vacuole of the cells, most probably as uranyl(VI) phosphates along with an intracellular sorption of U(VI) on biomembranes by lipid structures. Eu(III) could be found locally concentrated in the cell wall and in the cytoplasm with a co-localization with phosphorous and oxygen.