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.

How hydrothermal synthesis improves the synthesis of (Zr,Ce)SiO4 solid solutions.

Although ZrSiO4 is the most well-known compound in the zircon-structured family (space group I41/amd), the experimental conditions for preparing pure and well-crystallized phases that are doped with a tetravalent element via hydrothermal synthesis have never been clearly discussed in the literature. With the aim to answer this question, the experimental conditions of the preparation of ZrSiO4 and (Zr,Ce)SiO4 were investigated in order to synthesize well-crystallized and pure phases. A multiparametric study has been carried out using soft hydrothermal conditions with variables including reactant concentration, initial pH of the reactive medium, and duration of the hydrothermal treatment. Pure ZrSiO4 was obtained through hydrothermal treatment for 7 days at 250 °C, within a large acidity range (1.0 ≤ pH ≤ 9.0) and starting from CSi ≈ CZr ≥ 0.2 mol L-1. As hydrothermally prepared zircon structured phases can be both hydrated and hydroxylated, its annealed form was also studied after heating to 1000 °C. Based on these results, the synthesis of (Zr,Ce)SiO4 solid solutions was also investigated. The optimal hydrothermal conditions to acquire pure and crystallized phases were as follows: 7 days at 250 °C with initial pH = 1 and concentration of the reactants equal to 0.2 mol L-1. This led to Zr1-xCexSiO4 solid solutions with the incorporated Ce content up to 40 mol%. Samples were characterized using multiple methods, including laboratory and synchrotron PXRD, IR and Raman spectroscopies, SEM, and TGA. Moreover, it was found that these phases were thermally stable in air up to at least 1000 °C.

Time-resolved laser-induced fluorescence spectroscopy and chemometrics for fast identification of U(VI)-bearing minerals in a mining context.

We evaluated the potential of time-resolved laser-induced fluorescence spectroscopy (TRLFS) combined with chemometric methods for fast identification of U(VI)-bearing minerals in a mining context. We analyzed a sample set which was representative of several environmental conditions. The set consisted of 80 uranium-bearing samples related to mining operations, including natural minerals, minerals with uranium sorbed on the surface, and synthetic phases prepared and characterized specifically for this study. The TRLF spectra were processed using the Ward algorithm and the K-nearest neighbors (KNN) method to reveal similarities between samples and to rapidly identify the uranium-bearing phase and the associated mineralogical family. The predictive models were validated on an independent dataset, and then applied to test samples mostly taken from U mill tailings. Identification results were found to be in accordance with the available characterization data from X-ray diffraction (XRD) and scanning electron microscopy-energy dispersive X-ray spectrometry (SEM-EDX). This work shows that TRLFS can be an effective decision-making tool for environmental investigations or geological prospection, considering the large diversity of uranium-bearing mineral phases and their low concentration in environmental samples.

Correction: Formation of plutonium(IV) silicate species in very alkaline reactive media.

Correction for 'Formation of plutonium(IV) silicate species in very alkaline reactive media' by Paul Estevenon et al., Dalton Trans., 2021, 50, 12528-12536, DOI: 10.1039/D1DT02248B.

Formation of plutonium(IV) silicate species in very alkaline reactive media.

Studying the speciation of Pu(IV) in very alkaline and silicate ion rich reactive media allowed identification of the formation of plutonium(IV)-silicate colloidal suspensions which were stable for months. These colloids were stabilized in aqueous solution for pH > 13 and for concentrations around 10-2 mol L-1. Successive filtration processes allowed evaluation of their size, which was found to be smaller than 6 nm. Their structural characterization by XAS evidenced that their structure was similar to those identified for the other tetravalent actinide-silicate colloidal systems like thorium, uranium and neptunium. Their formation could explain the increase of plutonium solubility usually observed in alkaline silicate-rich solutions and could affect the plutonium mobility as a result in contaminated sites or in other environmental permeable media.

Effect of Annealing on Structural and Thermodynamic Properties of ThSiO4-ErPO4 Xenotime Solid Solution.

The effect of annealing on structural and thermochemical properties of a thorite-xenotime solid solution Th1-xErx(SiO4)1-x(PO4)x was assessed. The samples synthesized at low temperatures and stored at room temperature for 2 years retained their tetragonal structures. This structure was also maintained after heating to 1100 °C. During annealing, the structure lost water and exsolved some thorianite phases. The thermodynamic parameters did not change much after annealing, suggesting that xenotime was not a low-temperature metastable phase but rather a stable structure able to withstand elevated temperatures regardless of the thorium content. The solid solution exhibited subregular behavior with the Margules function W(x) = (73.1 ± 20.1) - (125.7 ± 49.8)·x.

The Role of Water and Hydroxyl Groups in the Structures of Stetindite and Coffinite, MSiO4 (M = Ce, U).

Orthosilicates adopt the zircon structure types (I41/amd), consisting of isolated SiO4 tetrahedra joined by A-site metal cations, such as Ce and U. They are of significant interest in the fields of geochemistry, mineralogy, nuclear waste form development, and material science. Stetindite (CeSiO4) and coffinite (USiO4) can be formed under hydrothermal conditions despite both being thermodynamically metastable. Water has been hypothesized to play a significant role in stabilizing and forming these orthosilicate phases, though little experimental evidence exists. To understand the effects of hydration or hydroxylation on these orthosilicates, in situ high-temperature synchrotron and laboratory-based X-ray diffraction was conducted from 25 to ∼850 °C. Stetindite maintains its I41/amd symmetry with increasing temperature but exhibits a discontinuous expansion along the a-axis during heating, presumably due to the removal of water confined in the [001] channels, which shrink against thermal expansion along the a-axis. Additional in situ high-temperature Raman and Fourier transform infrared spectroscopy also confirmed the presence of the confined water. Coffinite was also found to expand nonlinearly up to 600 °C and then thermally decompose into a mixture of UO2 and SiO2. A combination of dehydration and dehydroxylation is proposed for explaining the thermal behavior of coffinite synthesized hydrothermally. Additionally, we investigated high-temperature structures of two coffinite-thorite solid solutions, uranothorite (UxTh1-xSiO4), which displayed complex variations in composition during heating that was attributed to the negative enthalpy of mixing. Lastly, for the first time, the coefficients of thermal expansion of CeSiO4, USiO4, U0.46Th0.54SiO4, and U0.9Th0.1SiO4 were determined to be αV = 14.49 × 10-6, 14.29 × 10-6, 17.21 × 10-6, and 17.23 × 10-6 °C-1, respectively.

Thermodynamics of CeSiO4: Implications for Actinide Orthosilicates.

Zircon (ZrSiO4, I41/amd) can accommodate actinides, such as thorium, uranium, and plutonium. The zircon structure has been determined for several of the end-member compositions of other actinides, such as plutonium and neptunium. However, the thermodynamic properties of these actinide zircon structure types are largely unknown due to the difficulties in synthesizing these materials and handling transuranium actinides. Thus, we have completed a thermodynamic study of cerium orthosilicate, stetindite (CeSiO4), a surrogate of PuSiO4. For the first time, the standard enthalpy of formation of CeSiO4 was obtained by high temperature oxide melt solution calorimetry to be -1971.9 ± 3.6 kJ/mol. Stetindite is energetically metastable with respect to CeO2 and SiO2 by 27.5 ± 3.1 kJ/mol. The metastability explains the rarity of the natural occurrence of stetindite and the difficulty of its synthesis. Applying the obtained enthalpy of formation of CeSiO4 from this work, along with those previously reported for USiO4 and ThSiO4, we developed an empirical energetic relation for actinide orthosilicates. The predicted enthalpies of formation of AnSiO4 are then determined with a discussion of future strategies for efficiently immobilizing Pu or minor actinides in the zircon structure.

In situ study of the synthesis of thorite (ThSiO4) under environmental representative conditions.

Thorite, (ThSiO4) with a zircon type structure, is one of the most abundant natural sources of thorium on Earth. Generally, actinides are known to form nanoparticles in silicate medium, though no direct link between those colloids and the crystalline form of thorite was evidenced until now. Here we show the formation of thorite from colloids and nanocrystalline structures under experimental conditions close to environmental pH and temperature. Through in situ small and wide angle X-ray scattering (SWAXS) measurements, colloids with a few nanometers in size were first evidenced at a low reaction time. These colloids have elongated shapes and finally tend to aggregate after their size has reached 10 nm. Once aggregated, the system goes through a maturation step, ending with the emergence of nanocrystallites as thorite zircon structures. This maturation step is longer when the reaction temperature is decreased which highlights the kinetic considerations. These results have potential implications on the paragenesis of Th mineral deposits and also in the behaviour of Th and, by analogy, tetravalent actinides in the environment. The significant characteristics of this work are that Th-silicate colloids were demonstrated at low temperatures and a near neutral pH with long-term stability and a morphology in favor of high mobility in groundwater. If these species are formed in more diluted media, this could be problematic owing to the spreading of Th and, by analogy, other tetravalent actinides in the environment.

Coffinite formation from UO2+x.

Most of the highly radioactive spent nuclear fuel (SNF) around the world is destined for final disposal in deep-mined geological repositories. At the end of the fuel's useful life in a reactor, about 96% of the SNF is still UO2. Thus, the behaviour of UO2 in SNF must be understood and evaluated under the weathering conditions of geologic disposal, which extend to periods of hundreds of thousands of years. There is ample evidence from nature that many uranium deposits have experienced conditions for which the formation of coffinite, USiO4, has been favoured over uraninite, UO2+x, during subsequent alteration events. Thus, coffinite is an important alteration product of the UO2 in SNF. Here, we present the first evidence of the formation of coffinite on the surface of UO2 at the time scale of laboratory experiments in a solution saturated with respect to amorphous silica at pH = 9, room temperature and under anoxic conditions.

The formation of PuSiO4 under hydrothermal conditions.

Attempts to synthesize plutonium(iv) silicate, PuSiO4, have been made on the basis of results recently reported in the literature for CeSiO4, ThSiO4, and USiO4 under hydrothermal conditions. Although it was not possible to prepare PuSiO4via applying the conditions reported for thorium and uranium, an efficient method of PuSiO4 synthesis was established by applying the conditions optimized for the CeSiO4 system. This method was based on the slow oxidation of plutonium(iii) silicate reactants under hydrothermal conditions at 150 °C in hydrochloric acid (pH = 3-4). These results shed new light on the potential behavior of plutonium in reductive environments, highlighting the representative nature of cerium surrogates when studying plutonium under such conditions and providing some important pieces of information regarding plutonium chemistry in silicate solutions.

Uranium removal from mining water using Cu substituted hydroxyapatite.

In this study, synthetic copper substituted hydroxyapatite (Cu-Hap), CuxCa10-x(PO4)6(OH)2 were prepared by co-precipitation method and were used as reactive materials in batch experiments to immobilize uranyl. The limit of incorporation of Cu into a single-phased Cu-Hap reached xCu ≤1.59. The synthetic Cu-Hap samples obtained with various Cu contents were contacted with synthetic uranyl doped solutions and with real mining waters showing various pH and chemical compositions. A fast and strong decrease of the uranium concentration was observed, followed by the establishment of an equilibrium after 1-4 days of contact with the solutions. Examination of the solid phase after uranium uptake was performed using a combination of techniques. Depending on the composition of the solution and the copper content of the Cu-Hap, various mechanisms of uranium removal were observed. Based on the experimental results and geochemical simulations, it appeared that the main interest for using Cu-Hap is to enlarge the domain of water compositions for which the precipitation of meta-torbernite, (H3O)0.4Cu0.8(UO2)2(PO4)2·7.6 H2O is the predominant mechanism associated to the uranium removal, especially for pH > 6.7 where carbonate uranium species are predominant.

Formation of CeSiO4 from cerium(iii) silicate precursors.

Although the preparation of CeSiO4 has been already reported, the formation of pure cerium silicate from aqueous precursors appears as a challenge. An innovative way of synthesis has been identified in this study, allowing the formation of CeSiO4 after hydrothermal treatment starting from Ce(iii) silicate precursors. Among the experimental parameters examined, significant effects were found according to the nature of the precursor and of the reactive media considered, the pH of the reactive media and the temperature of the hydrothermal process. This study allows the determination of optimized conditions for the hydrothermal synthesis of pure CeSiO4 (A-Ce2Si2O7 or Ce4.67(SiO4)3O as starting precursors, nitric medium, pH = 7, 7 days at 150 °C). The in situ low oxidation rate of Ce(iii) into Ce(iv) was a key parameter to consider in order to avoid the presence of CeO2 in the final mixtures.

Preparation of CeSiO4 from aqueous precursors under soft hydrothermal conditions.

Even though CeSiO4 was synthesized one time through a hydrothermal treatment, the conditions leading to its formation remain largely unknown. In order to define the optimized conditions of synthesis, a multiparametric study was developed by varying the pH of the solution, the temperature, and the nature of the reactants and of the complexing ions in solution. This study highlighted that CeSiO4 could not be obtained starting from Ce(iv) reactants. An optimal set of conditions was defined to prepare single phase samples. Pure CeSiO4 was obtained through a hydrothermal treatment at 150 °C using a starting mixture of 1 mol L-1 Ce(iii) nitrate and Na2SiO3 solutions and by adjusting the initial pH to 8. The chemical limitations observed during the synthesis of CeSiO4 suggested that the formation of this phase may result from the slow in situ oxidation of a Ce(iii) silicate complex during the hydrothermal treatment.

Impact of Carbonate Ions on the Synthesis of ThSiO4 under Hydrothermal Conditions.

Multiparametric study of the hydrothermal synthesis of thorite, ThSiO4, was performed with the aim to determine the most efficient conditions to form single phase thorite samples. Among the experimental parameters investigated, temperature of the hydrothermal process, concentration of carbonate ions, thorium and silicon reactants, and pH of the reactive media significantly affect the composition of the final system obtained. Single phase samples of ThSiO4 were prepared in weakly basic reactive media and at temperatures over 150 °C, for thorium and silicate concentrations higher than 8 × 10-3 mol L-1 and carbonate concentrations of at least 8 × 10-2 mol L-1. Although the synthesis of thorite in carbonate media was already described in the literature, this study gives new insights to explain the key role of carbonate ions in the preparation of thorite. Especially, beyond their simple role of pH buffer, carbonate ions are involved in the formation of thorium-carbonate complexes at high pH, increasing the apparent solubility of thorium in weakly basic media. The presence of carbonate ions has an important impact not only on the domain of formation of thorite but also on the morphology of the silicate phase.

Multiparametric Study of the Synthesis of ThSiO4 under Hydrothermal Conditions.

A multiparametric study of the hydrothermal synthesis of ThSiO4, thorite, was performed with the aim of determining the most efficient conditions to form single-phase samples. Among the experimental parameters examined, significant effects were found for the concentration of reactants in the starting mixture, pH of the reactive media, and temperature of the hydrothermal process. Such parameters affected both the rate of formation of thorite and the morphology of the final products synthesized. Precipitation of pure ThSiO4 was obtained over a wide range of pH on going from CHNO3 = 0.3 mol L-1 to pH 9.1 with a yield of over 95%. Temperatures higher than 160 °C favor the formation of thorite. Finally, thorium and silicon concentrations above 2.1 × 10-3 mol L-1 are required to obtain pure thorium silicate.

Thermodynamics and Stability of Rhabdophanes, Hydrated Rare Earth Phosphates REPO4 · n H2O.

Rare earth phosphates comprise a large family of compounds proposed as possible nuclear waste disposal forms. We report structural and thermodynamic properties of a series of rare earth rhabdophanes and monazites. The water content of the rhabdophanes, including both adsorbed and structural water, decreases linearly with increase in ionic radius of the rare earth. The energetics of the transformation of rhabdophane to monazite plus water and the enthalpy of formation of rhabdophane from the constituent oxides was determined by high temperature drop solution calorimetry. The former varies linearly with the ionic radius of the lanthanide, except for cerium. By combining the enthalpy of formation determined by high temperature drop solution calorimetry and the free energy of formation determined previously by solubility experiments, a complete set of thermodynamic data was derived for the rhabdophanes. They are thermodynamically metastable with respect to the corresponding monazites plus water at all temperatures under ambient pressure conditions. This conclusion strengthens the case for monazites being an excellent nuclear waste form.

Incorporation of Thorium in the Zircon Structure Type through the Th1-xErx(SiO4)1-x(PO4)x Thorite-Xenotime Solid Solution.

Pure powdered compounds with a general formula Th1-xErx(SiO4)1-x(PO4)x belonging to the zircon-xenotime family were successfully synthesized under hydrothermal conditions (250 °C, 7 days) as recently reported for the preparation of coffinite. Therefore, a thorough, combined PXRD, EDX, EXAFS, Raman, and FTIR analysis showed the formation of a solid solution in agreement with Vegard's law. Moreover, the examination of the local structure shows that the Th-O distances remain close to those found in ThSiO4, whereas the Er-O distances show a significant decrease from 2.38(14) to 2.34(7) Å when increasing the erbium content from x = 0.2 to x = 1. The variation of the local structure also affects the PO43- groups that are surely distorted in the structure.

Coffinite, USiO4, Is Abundant in Nature: So Why Is It So Difficult To Synthesize?

Coffinite, USiO4, is the second most abundant U(4+) mineral on Earth, and its formation by the alteration of the UO2 in spent nuclear fuel in a geologic repository may control the release of radionuclides to the environment. Despite its abundance in nature, the synthesis and characterization of coffinite have eluded researchers for decades. On the basis of the recent synthesis of USiO4, we can now define the experimental conditions under which coffinite is most efficiently formed. Optimal formation conditions are defined for four parameters: pH, T, heating time, and U/Si molar ratio. The adjustment of pH between 10 and 12 leads probably to the formation of a uranium(IV) hydroxo-silicate complex that acts as a precursor of uranium(IV) silicate colloids and then of coffinite. Moreover, in this pH range, the largest yield of coffinite formation (as compared with those of the two competing byproduct phases, nanometer-scale UO2 and amorphous SiO2) is obtained for 250 °C, 7 days, and 100% excess silica.

Thermodynamics of formation of coffinite, USiO4.

Coffinite, USiO4, is an important U(IV) mineral, but its thermodynamic properties are not well-constrained. In this work, two different coffinite samples were synthesized under hydrothermal conditions and purified from a mixture of products. The enthalpy of formation was obtained by high-temperature oxide melt solution calorimetry. Coffinite is energetically metastable with respect to a mixture of UO2 (uraninite) and SiO2 (quartz) by 25.6 ± 3.9 kJ/mol. Its standard enthalpy of formation from the elements at 25 °C is -1,970.0 ± 4.2 kJ/mol. Decomposition of the two samples was characterized by X-ray diffraction and by thermogravimetry and differential scanning calorimetry coupled with mass spectrometric analysis of evolved gases. Coffinite slowly decomposes to U3O8 and SiO2 starting around 450 °C in air and thus has poor thermal stability in the ambient environment. The energetic metastability explains why coffinite cannot be synthesized directly from uraninite and quartz but can be made by low-temperature precipitation in aqueous and hydrothermal environments. These thermochemical constraints are in accord with observations of the occurrence of coffinite in nature and are relevant to spent nuclear fuel corrosion.