Adsorption of uranyl to SWy-1 montmorillonite was evaluated experimentally and results were modeled to identify likely surface complexation reactions responsible for removal of uranyl from solution. Uranyl was contacted with SWy-1 montmorillonite in a NaCIO4 electrolyte solution at three ionic strengths (I = 0.001, 0.01, 0.1), at pH 4 to 8.5, in a N2(g) atmosphere. At low ionic strength, adsorption decreased from 95% at pH 4 to 75% at pH 6.8. At higher ionic strength, adsorption increased with pH from initial values less than 75%; adsorption edges for all ionic strengths coalesced above a pH of 7. A site-binding model was applied that treated SWy-1 as an aggregate of fixed-charge sites and edge sites analogous to gibbsite and silica. The concentration of fixed-charge sites was estimated as the cation exchange capacity, and non-preference exchange was assumed in calculating the contribution of fixed-charge sites to total uranyl adsorption. The concentration of edge sites was estimated by image analysis of transmission electron photomicrographs. Adsorption constants for uranyl binding to gibbsite and silica were determined by fitting to experimental data, and these adsorption constants were then used to simulate SWy-1 adsorption results. The best simulations were obtained with an ionization model in which AlOH2+ was the dominant aluminol surface species throughout the experimental range in pH. The pH-dependent aqueous speciation of uranyl was an important factor determining the magnitude of uranyl adsorption. At low ionic strength and low pH, adsorption by fixed-charge sites was predominant. The decrease in adsorption with increasing pH was caused by the formation of monovalent aqueous uranyl species, which were weakly bound to fixed-charge sites. At higher ionic strengths, competition with Na+ decreased the adsorption of UO22+ to fixed-charge sites. At higher pH, the most significant adsorption reactions were the binding of UO22+ to AlOH and of (UO2)3(OH)5+ to SiOH edge sites. Near-saturation of AlOH sites by UO22+ allowed significant contributions of SiOH sites to uranyl adsorption.

The sorption of the uranyl oxo-cation (UO22+)at different types of binding sites on layer silicate mineral surfaces was investigated. Well-characterized samples of vermiculite and hydrobiotite were exposed to aqueous uranyl under conditions designed to promote surface sorption either at fixed charge ionexchange sites or at amphoteric surface hydroxyl sites. The local structure of uranium in the sorption samples was directly measured using uranium L3-edge extended X-ray absorption fine structure (EXAFS). Polarized L1- and L3-edge X-ray absorption near-edge structure (XANES) measurements were used to characterize the orientation of uranyl groups in layered samples. X-ray diffraction (XRD) measurements of interlayer spacings were used to assess the effects of ion-exchange and dehydration upon the mineral structure. The most significant findings are: (1) Under conditions which greatly favor ion-exchange sorption mechanisms, uranyl retains a symmetric local structure suggestive of an outer-sphere complex, with a preferred orientation of the uranyl axis parallel to the mineral layers; (2) Upon dehydration, the ionexchange complexes adopt a less symmetric structure, consistent with an inner-sphere complex, with less pronounced orientation of the uranyl axis; and (3) For conditions which favor sorption at surface hydroxyl sites, uranyl has a highly distorted equatorial shell, indicative of stronger equatorial ligation, and the detection of a neighboring U atom suggests the formation of surface precipitates and/or oligomeric complexes.

We report a combined experimental and theoretical study of uranyl complexes that form on the interlayer siloxane surfaces of montmorillonite. We also consider the effect of isomorphic substitution on surface complexation since our montmorillonite sample contains charge sites in both the octahedral and tetrahedral sheets. Results are given for the two-layer hydrate with a layer spacing of 14.58 Å. Polarized-dependent X-ray absorption fine structure spectra are nearly invariant with the incident angle, indicating that the uranyl ions are oriented neither perpendicular nor parallel to the basal plane of montmorillonite. The equilibrated geometry from Monte Carlo simulations suggests that uranyl ions form outer-sphere surface complexes with the [O=U=O]2+ axis tilted at an angle of ~45° to the surface normal.

We performed Monte Carlo and molecular dynamics simulations to investigate the interlayer structure of a uranyl-substituted smectite clay. Our clay model is a dioctahedral montmorillonite with negative charge sites in the octahedral sheet only. We simulated a wide range of interlayer water content (0 mg H2O/g clay — 260 mg H2O/g clay), but we were particularly interested in the two-layer hydrate that has been the focus of recent X-ray absorption experiments. Our simulation results for the two-layer hydrate of uranyl-montmorillonite yield a water content of 160 mg H2O/g clay and a layer spacing of 14.66 Å. Except at extremely low water content, uranyl cations are oriented nearly parallel to the surface normal in an outer-sphere complex. The first coordination shell consists of five water molecules with an average U-O distance of 2.45 Å, in good agreement with experimental data. At low water content, the cations can assume a perpendicular orientation to include surface oxygen atoms in the first coordination shell. Our molecular dynamics results show that ${\text{UO}}_2{\left({\text{H}}_2\text{O}\right)}_5^{2+}$ complexes translate within the clay pore through a jump diffusion process, and that first-shell water molecules are exchangeable and interchangeable.

Adsorption of uranyl (UO22+) ions to mineral surfaces is a potentially effective method for removing this hazardous metal from water, but other toxic trace metal ions (Xn+: Rb+, Sr2+, Cr3+, Mn2+, Ni2+, Zn2+, Cd2+) in uraniferous wastewaters compete with UO22+ for adsorption sites and thus may diminish the capacity of adsorbents to sequester UO22+. A better understanding of competitive adsorption among these metal ions and the development of better adsorbents are, therefore, of critical importance. The purpose of the present study was to synthesize and characterize magnetic adsorbents, consisting of MFe2O4 (M = Mn, Fe, Zn, Co, or Ni) nanoparticles synthesized on montmorillonite (Mnt) edge sites, and to investigate their use as adsorbents for UO22+, including competitive adsorption with trace metal ions. Selective adsorption was studied using Langmuir, Freundlich, and Dubinin-Radushkevich isotherms, and the results showed that Xn+ ions were adsorbed primarily on MFe2O4-montmorillonite surfaces, and the UO22+ ions were adsorbed on the interfaces between montmorillonite edge surfaces and MFe2O4 nanoparticles. Using the Freundlich model, the interface adsorption capacity of UO22+ reached 25.1 mg·g–1 in mixed solution. Further, the UO22+ and Cr3+ ions had a redox reaction on the interfaces with synergistic adsorption. Herein, the adsorption capacity of Cr3+ was 60.2 mg·g–1 using the Freundlich isotherm. The results demonstrated that the MFe2O4-montmorillonite with highly selective adsorption of UO22+ ions is applicable to UO22+ treatment in the presence of toxic trace metal ions.

Graphical abstract

Sorption of U(VI) on clay and related minerals has been inspected experimentally and computationally because of its central role in safety considerations of geological repositories for highly radioactive waste. Np(V), which also has long half-life isotopes, has received considerably less attention. The purpose of the present study was to investigate computationally the adsorption of Np(V) on a clay-mineral surface and to compare it to adsorption of U(VI). As a sample case study, adsorption of Np(V) at the (110) edge surface of the common clay mineral montmorillonite was modeled. The density functional approach and periodic supercell models were applied. Mono- and bidentate adsorption complexes with coordination numbers 4 and 5 were inspected and compared to corresponding U(VI) species. While U(VI) prefers bidentate adsorption complexes with varying coordination numbers, Np(V) is more stable when monodentate-coordinated with a coordination number of four. In line with its smaller hydrolysis constant in aqueous solution, Np(V) shows a lower tendency to form monohydroxides on the mineral surface compared to U(VI). As no experimental geometry parameters are available for Np(V) adsorbed on montmorillonite, the results were compared tentatively to EXAFS data for adsorption at kaolinite and good agreement for the geometry changes due to adsorption was found for the more preferred adsorbed species.

The results of combined single-crystal X-ray diffraction, electron probe microanalysis, Fourier microspectroscopy, and photoluminescence spectroscopy study of crystals of turkestanite from the Dara-i-Pioz deposit, Tien-Shan Mountains, Tajikistan are reported. It is a single-layer sheet silicate belonging to the ekanite group with a steacyite structural type. Averaged major-element analysis provided (wt.%): K2O 4.13(6), CaO 8.1(1), Na2O 2.3(1), ThO2 25.8(4), UO2 3.6(4) and SiO2 55.9(1). The averaged crystal-chemical formula for the studied turkestanite is (Th0.84U0.12)Σ0.96(Ca1.24Na0.65)Σ1.89(K0.75☐0.25)Σ1.00Si8O19.72(OH)0.28. Single-crystal structural refinement of turkestanite gave tetragonal, space group P4/mcc, a = 7.5708(3) Å, c = 14.7300(11) Å, V = 844.27(6) Å3 and Z = 2. Luminescence of the uranyl ion (UO2)2+ is observed in turkestanite. In the excitation spectrum, the bands corresponding to a charge transfer transition from the 2p states of the ligand to the 5f state of uranium were found.

The sorption behaviour of I−, Cs+, Ni2+, Eu3+, Th4+ and UO2+ 2on NRVB (Nirex reference vault backfill) a possible vault backfill, at pH 12.8 was studied. Sorption isotherms generated were compared to results obtained in the presence of cellulose degradation products (CDP). Whereas Cs was not affected by the presence of the organic compounds, a notable reduction in the sorption of Th and Eu to cement was observed. The results also indicated limited removal of Ni from solution (with or without an organic ligand) by sorption, the concentration in solution seemingly being determined solely by solubility processes. In the case of uranium, the presence of CDP increased the sorption to cement by almost one order of magnitude. Further studies into the uptake of CDP by cement are being undertaken to identify the mechanism(s) responsible.

A systematic investigation of agates from different occurrences in Europe, Northern and Southern America reveals that macrocrystalline quartz and chalcedony within them have an unusually high uranium content. Whereas agates may contain >70 ppm of U, quartz from magmatic and metamorphic rocks as well as pegmatite quartz commonly exhibit U concentrations at sub-ppm levels. Spatially resolved trace-element analyses by laser ablation inductively coupled plasma mass spectrometry show that the distribution of U within the agate samples is heterogeneous and coincides with the structural banding. The results indicate that U is incorporated into agate as uranyl ions. These ions, which are bound to the silica surface, are interpreted to originate from the parallel accumulation of Si and U by alteration processes of surrounding host rocks during agate formation.

The uranyl ion is the cause of greenish photoluminescence (PL) in agate, which can only be excited by short wavelengths (<300 nm). The green PL is due to the electron transition from an excited to a ground state of the uranyl ion and is shown by a typical emission line at ∼500 nm accompanied by several equidistant lines. These are due to the harmonic vibration of oxygen atoms along the uranyl axis. Luminescence can be detected in samples with a U content down to the 1 ppm level.