www.nature.com/scientificreports OPEN Cofnite formation from ­UO2+x Stéphanie Szenknect1*, Delhia Alby1, Marta López García2, Chenxu Wang4, Renaud Podor1, Frédéric Miserque5, Adel Mesbah1, Lara Duro2, Lena Zetterström Evins3, Nicolas Dacheux1, Jordi Bruno2 & Rodney C. Ewing4 Most of the highly radioactive spent nuclear fuel (SNF) around the world is destined for fnal 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 cofnite, USiO4, has been favoured over uraninite, UO2+x, during subsequent alteration events. Thus, cofnite is an important alteration product of the UO2 in SNF. Here, we present the frst evidence of the formation of cofnite 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. 4+ Uraninite, UO2+x is the most common U mineral in nature followed by cofnite, USiO 4, which is found as a primary phase or an alteration product in many uranium deposits. Cofnite, tetragonal, is isostructural with 1 zircon (ZrSiO4) and thorite (TSiO 4); however, cofnite can contain some water either as H 2O or OH groups . Altered uraninite and cofnite have been documented from Oklo, Gabon 2–5, deposits in the Athabasca Basin 4,6,7 and Elliot Lake, Canada8. Other examples include Jachymov, Czech Republic9 or La Crouzille district, France10. For many years, cofnite had gone unrecognized in most uranium deposits, particularly uranium roll-front deposits, as a distinct phase because of its fne grain size and intimate association with uraninite 5,6,11,12. Te alteration of uraninite to cofnite is a key event for UO 2 in nature and UO 2 in spent fuel in a geologic repository. Cofnite, being a U4+-silicate, is associated with reducing environments, with sulphides and organic matter1, where it likely precipitated from neutral to weakly alkaline fuids. Cofnite formation in sedimentary uranium deposits is associated with relatively low temperatures, 80–130 °C. A detailed investigation of meteoric roll-front deposits in the Athabasca basin, suggest an estimated temperature of cofnite precipitation in the uranium front of no greater than 50 °C13. Even though laboratory experiments report cofnite formation at 150–250 °C14,15, it appears that these elevated temperatures are not required to form cofnite in nature. Although cofnite is abundant in uranium ore deposits, its synthesis has been a major challenge since its initial description as a mineral in 195516. A number of investigators have sought to obtain pure synthetic cofnite, but only a few have succeeded14,15,17–21. Synthetic cofnite was always obtained under hydrothermal conditions. Systematically, the samples obtained were a mixture of phases, mainly composed of fne grains of USiO4, nano- particles of UO2 and amorphous SiO2. All of these attempts to synthesize cofnite indicate that there is only a narrow range in terms of temperature, pH, uranium and silicate ions concentrations and oxygen fugacity for which the formation of cofnite over UO 2 is favored. More recently, the determination of thermodynamic data 22,23 has been made possible thanks to the preparation of a single-phase USiO4 sample . Tese data confrm the relative stability of cofnite and UO 2 as a function of groundwater composition. Termodynamic calculations indicate unambiguously that cofnite is less stable than the quartz and UO 2 (cr) mixture at 25 °C. However, cofnite precipitates in solutions undersaturated with respect to amorphous UO 2⋅2H2O (am) in silicate solu- –5 –3 −1 24 tions with concentrations typical of groundwater (i.e.[Si]tot between 7 × 10 and 5 × 10 mol L ) . Tis result supports the idea that the uraninite-cofnite transformation requires a prior destabilization of uraninite and that this could be caused by self-irradiation, leading to metamictization of the solid and radiolysis of water and/ or surface oxidation at moderate oxygen fugacities. Non-stoichiometry is also common in natural uraninite and 1ICSM, Univ Montpellier, CEA, CNRS, ENSCM, 30207 Bagnols sur Cèze, France. 2Amphos 21, Consulting, Carrer Veneçuela, 103, Planta 2, 08019 Barcelona, Spain. 3Swedish Nuclear Fuel and Waste Management Co, Blekholmstorget 30, 101 24 Stockholm, Sweden. 4Department of Geological Sciences, Stanford University, Stanford, CA 94305-2115, USA. 5DES-Service de la Corrosion et du Comportement des matériaux dans leur Environnement (SCCME), CEA, Université Paris-Saclay, 91191 Gif-Sur-Yvette, France. *email: [email protected] SCIENTIFIC REPORTS | (2020) 10:12168 | https://doi.org/10.1038/s41598-020-69161-1 1 Vol.:(0123456789) www.nature.com/scientificreports/ Figure 1. (a) U-4f core levels XPS spectrum of UO2 pellet before leaching. (b) SEM micrograph (BSE mode) of the surface of the UO2 pellet before leaching experiment. Scale bar 50 µm. could have a signifcant efect on uraninite reactivity and solubility9. Cofnite could thus be preferentially formed at the interface between UO2+x resulting from the oxidation of UO2 surface layer and the silicate-bearing fuids. Similar to natural uraninite, recent fndings regarding the thermodynamic stability of cofnite have renewed the interest in considering cofnite as a potential alteration product of SNF in a geologic repository, particularly under reducing conditions. During in-reactor irradiation UO2 fuel pellets experience many chemical modifca- tions and considerable radiation-induced defect formation. Such microstructural changes in UO2 matrix occur from the nanometer up to the macroscopic scale25 and, by similar to uraninite, could enhance the possibility of the formation of cofnite26. Most of the geologic sites under investigation for underground repositories are –4 located in undisturbed clay-rich rock or granite, with silica-rich groundwaters ([Si]tot ~ 10 mol/L), deep enough to have reducing conditions (typical Eh range from − 50 to − 300 mV)27,28. Understanding the interaction of used fuel with the silicate-rich groundwaters is critical to evaluate the safety of diferent disposal strategies, as the cofnitization process has not been considered until now. In this paper: • We show for the frst time, at laboratory time scale, the formation of cofnite from UO2 in the presence of solution saturated with respect to SiO2(am) under conditions typical of near-surface uranium deposits and deep-mined geologic repositories for SNF. • We have constrained the conditions of formation in an Eh–pH diagram where the precipitation of cofnite is favoured over UO2⋅2H2O (am). • We show that cofnite precipitation could lower the uranium release from the UO 2 matrix of SNF through oxidative weathering in the presence of oxygen in the geological repository. • Dissolution assisted by silicate ions and precipitation under slightly oxidative conditions (i.e., Eh between -100 and + 100 mV) explains the coexistence of uraninite and cofnite in uranium ore deposits. Experimental results UO2 powder was synthesized, then sintered under reducing conditions to maintain uranium in the tetravalent oxidation state. UO 2 individual pellet was characterized by X-ray difraction (XRD), scanning electron micros- copy (SEM) and X-ray photoelectron spectroscopy (XPS). Details of the synthesis and characterization are included in the “Experimental methods” section. For the pellet treated at high temperature under vacuum, the value of the unit cell parameter obtained by Rietveld refnement was: a = 546.95(1) pm (Fig. S1 of the supporting information). Tis value was compared 29 with the unit cell parameter determined by Leinders et al. for stoichiometric UO2 (a = 547.127 (8) pm). Tis indicates that the sintered pellet has not oxidized to UO 2+x. However, three main contributions were needed to ft the experimental U-4f7/2 core level XPS spectrum of UO2 pellet (Fig. 1a). Tese contributions were attributed 4+ 5+ 6+ to U , U and U oxidation states with U-4f7/2 peak binding energies of 379.7 ± 0.3 eV; 380.8 ± 0.3 eV and 382.3 ± 0.3 eV, respectively14,30. Te presence of shake-up satellite peaks at 6.8 eV and 8.1 eV from the main 4+ 5+ + U-4f7/2 peaks showed that uranium oxidation states were mainly U and U . In situ Ar ion etching led to U-4f core levels spectrum with only one U 4+ contribution. Tis confrmed that uranium in the bulk material was U 4+, while U5+ and U 6+ were only present as a thin oxidation layer at the pellet surface. SEM images of the pellet before leaching (Fig. 1b) showed large grains of 10–25 µm in size. Grain “pull-out” was also observed and attributed to the polishing step. Tis grain pull-out contributed to the signifcant increase of the open porosity in the pellet, and thus an increased reactive surface area. Tis pellet was leached at room temperature, under anoxic conditions (pO2 ≤ 1 ppm), with a solution slightly –3 undersaturated with respect to amorphous silica at 25 °C and at pH = 8.76 (i.e.[Si]tot = (1.77 ± 0.03) × 10 mol SCIENTIFIC REPORTS | (2020) 10:12168 | https://doi.org/10.1038/s41598-020-69161-1 2 Vol:.(1234567890) www.nature.com/scientificreports/ Figure 2. Eh (a); pH (b); uranium (c) and silicate (d) elemental concentrations during the leaching of the UO2 pellet (open symbols represent data obtained afer ultrafltration of the solution). −1 –5 −1 L ), but oversaturated with respect to USiO4 cofnite (i.e.[U]tot = 10 mol L ). pH, Eh, Si and U elemental concentrations were monitored during the leaching experiment (Fig. 2). Te results in Fig. 2 indicate that the conditions stabilized afer 100 days of contact with the following average –3 −1 and standard deviation values: pH = 8.76 ± 0.03; Eh = − 55 ± 35 mV; [Si]tot = (1.41 ± 0.05) × 10 mol L .