Retention of selenium by calcium aluminate hydrate (AFm) phases under strongly-reducing radioactive waste repository conditions.

Safety assessment studies of future nuclear waste repositories carried out in many countries predict selenium-79 to be a critical radionuclide due to its presence as anion in three relevant oxidation states (vi, iv, -ii) resulting in weak retardation by most common rock minerals. This assumption, however, ignores its potential uptake by AFm phases, positively charged anion exchangers, which are present in significant quantities in the cementitious materials used in artificial barriers. Here we report for the first time wet chemistry and spectroscopic data on the interaction of the most relevant selenium anion species under the expected strongly reducing conditions, i.e. HSe-, with two AFm phases commonly found in cement, monocarbonate (AFm-MC) and hemicarbonate (AFm-HC). Batch sorption experiments showed that HSe- is retained much more strongly by AFm-HC (solid-liquid distribution ratio, Rd, of 100 ± 50 L kg-1) than by AFm-MC (Rd = 4 ± 2 L kg-1) at the equilibrium pH (∼12). X-ray absorption fine-structure (XAFS) spectroscopy revealed that the larger d-spacing in AFm-HC (d-spacing = 8.2 Å) provides easy access for HSe- to the AFm interlayer space for sorption, whereas the smaller d-spacing of AFm-MC (d-spacing = 7.55 Å) hinders interlayer access and limits HSe- sorption mostly to the outer planar surfaces and edges of the latter AFm phase. XAFS spectra further demonstrated that Se(-ii) prevalently sorbed in the interlayers of AFm-HC, is better protected from oxidation than Se(-ii) prevalently sorbed onto the outer surfaces of AFm-MC. The quantitative sorption data along with the molecular-scale process understanding obtained from this study provide crucial insight into the Se retention by the cementitious near-field of a radioactive waste repository under reducing conditions.

Biotransformation and detoxification of selenite by microbial biogenesis of selenium-sulfur nanoparticles.

This study combines the interaction between the toxic oxyanions selenite and selenate and the plant growth promoting bacterium Azospirillum brasilense with a comprehensive characterization of the formed selenium particles. As selenium is an essential trace element, but also toxic in high concentrations, its state of occurrence in nature is of major concern. Growth of the bacterium was affected by selenite (1-5mM) only, observable as a prolonged growth lag-phase of 3days. Subsequently, selenite reduction occurred under aerobic conditions resulting in extracellularly formed insoluble Se0 particles. Complementary studies by microscopic and spectroscopic techniques revealed the particles to be homogeneous and stable Se8-nSn structured spheres with an average size of 400nm and highly negative surface charge of -18mV in the neutral pH range. As this is the first study showing Azospirillum brasilense being able to biotransform selenite to selenium particles containing a certain amount of sulfur, even if environmental waters supplemented with selenite were used, they may significantly contribute to the biogeochemical cycling of both elements in soil as well as to their soil-plant transfer. Therefore, microbial biotransformation of selenite under certain circumstances may be used for various bio-remediation and bio-technological applications.

Sorption of trivalent lanthanides and actinides onto montmorillonite: Macroscopic, thermodynamic and structural evidence for ternary hydroxo and carbonato surface complexes on multiple sorption sites.

The credibility of long-term safety assessments of radioactive waste repositories may be greatly enhanced by a molecular level understanding of the sorption processes onto individual minerals present in the near- and far-fields. In this study we couple macroscopic sorption experiments to surface complexation modelling and spectroscopic investigations, including extended X-ray absorption fine structure (EXAFS) and time-resolved laser fluorescence spectroscopies (TRLFS), to elucidate the uptake mechanism of trivalent lanthanides and actinides (Ln/An(III)) by montmorillonite in the absence and presence of dissolved carbonate. Based on the experimental sorption isotherms for the carbonate-free system, the previously developed 2 site protolysis non electrostatic surface complexation and cation exchange (2SPNE SC/CE) model needed to be complemented with an additional surface complexation reaction onto weak sites. The fitting of sorption isotherms in the presence of carbonate required refinement of the previously published model by reducing the strong site capacity and by adding the formation of Ln/An(III)-carbonato complexes both on strong and weak sites. EXAFS spectra of selected Am samples and TRLFS spectra of selected Cm samples corroborate the model assumptions by showing the existence of different surface complexation sites and evidencing the formation of Ln/An(III) carbonate surface complexes. In the absence of carbonate and at low loadings, Ln/An(III) form strong inner-sphere complexes through binding to three Al(O,OH)6 octahedra, most likely by occupying vacant sites in the octahedral layers of montmorillonite, which are exposed on {010} and {110} edge faces. At higher loadings, Ln/An(III) binds to only one Al octahedron, forming a weaker, edge-sharing surface complex. In the presence of carbonate, we identified a ternary mono- or dicarbonato Ln/An(III) complex binding directly to one Al(O,OH)6 octahedron, revealing that type-A ternary complexes form with the one or two carbonate groups pointing away from the surface into the solution phase. Within the spectroscopically observable concentration range these complexes could only be identified on the weak sites, in line with the small strong site capacity suggested by the refined sorption model. When the solubility of carbonates was exceeded, formation of an Am carbonate hydroxide could be identified. The excellent agreement between the thermodynamic model parameters obtained by fitting the macroscopic data, and the spectroscopically identified mechanisms, demonstrates the mature state of the 2SPNE SC/CE model for predicting and quantifying the retention of Ln/An(III) elements by montmorillonite-rich clay rocks.

Multiscale structural characterizations of mixed U(iv)-An(iii) oxalates (An(iii) = Pu or Am) combining XAS and XRD measurements.

Mixed actinide(III,IV) oxalates of the general formula M2.2UAn(C2O4)5·nH2O (An = Pu or Am and M = H3O(+) and N2H5(+)) have been quantitatively precipitated by oxalic precipitation in nitric acid medium (yield >99%). Thorough multiscale structural characterization using XRD and XAS measurements confirmed the existence of mixed actinide oxalate solid solutions. The XANES analysis confirmed that the oxidation states of the metallic cations, tetravalent for uranium and trivalent for plutonium and americium, are maintained during the precipitation step. EXAFS measurements show that the local environments around U(+IV), Pu(+III) and Am(+III) are comparable, and the actinides are surrounded by ten oxygen atoms from five bidentate oxalate anions. The mean metal-oxygen distances obtained by XAS measurements are in agreement with those calculated from XRD lattice parameters.

The influence of metallic brazing materials on the strain formation of internally water-cooled X-ray optics.

A study of metallic brazing material for internally cooled optics is presented. The study shows the influence of the different material properties on the final quality of the bond in terms of diffracted wavefront distortion, i.e. enlargement of the rocking curve. By choosing the proper brazing material and applying the proper brazing conditions, the influence of the brazing material can be fully eliminated. Furthermore the degradation of some brazing material due to the extreme working conditions of the optics is presented. Measurement results from ESRF and KEK confirm the importance of the proper brazing material choice.

A 23Na magic angle spinning nuclear magnetic resonance, XANES, and high-temperature X-ray diffraction study of NaUO3, Na4UO5, and Na2U2O7.

The valence state of uranium has been confirmed for the three sodium uranates NaU(V)O3/[Rn](5f(1)), Na4U(VI)O5/[Rn](5f(0)), and Na2U(VI)2O7/[Rn](5f(0)), using X-ray absorption near-edge structure (XANES) spectroscopy. Solid-state (23)Na magic angle spinning nuclear magnetic resonance (MAS NMR) measurements have been performed for the first time, yielding chemical shifts at -29.1 (NaUO3), 15.1 (Na4UO5), and -14.1 and -19 ppm (Na1 8-fold coordinated and Na2 7-fold coordinated in Na2U2O7), respectively. The [Rn]5f(1) electronic structure of uranium in NaUO3 causes a paramagnetic shift in comparison to Na4UO5 and Na2U2O7, where the electronic structure is [Rn]5f(0). A (23)Na multi quantum magic angle spinning (MQMAS) study on Na2U2O7 has confirmed a monoclinic rather than rhombohedral structure with evidence for two distinct Na sites. DFT calculations of the NMR parameters on the nonmagnetic compounds Na4UO5 and Na2U2O7 have permitted the differentiation between the two Na sites of the Na2U2O7 structure. The linear thermal expansion coefficients of all three compounds have been determined using high-temperature X-ray diffraction: αa = 22.7 × 10(-6) K(-1), αb = 12.9 × 10(-6) K(-1), αc = 16.2 × 10(-6) K(-1), and αvol = 52.8 × 10(-6) K(-1) for NaUO3 in the range 298-1273 K; αa = 37.1 × 10(-6) K(-1), αc = 6.2 × 10(-6) K(-1), and αvol = 81.8 × 10(-6) K(-1) for Na4UO5 in the range 298-1073 K; αa = 6.7 × 10(-6) K(-1), αb = 14.4 × 10(-6) K(-1), αc = 26.8 × 10(-6) K(-1), αß = -7.8 × 10(-6) K(-1), and αvol = -217.6 × 10(-6) K(-1) for Na2U2O7 in the range 298-573 K. The α to ß phase transition reported for the last compound above about 600 K was not observed in the present studies, either by high-temperature X-ray diffraction or by differential scanning calorimetry.

Comparative EXAFS investigation of uranium(VI) and -(IV) aquo chloro complexes in solution using a newly developed spectroelectrochemical cell.

The coordination of the U(IV) and U(VI) ions as a function of the chloride concentration in aqueous solution has been studied by U L(III)-edge extended X-ray absorption fine structure (EXAFS) spectroscopy. The oxidation state of uranium was changed in situ using a gastight spectroelectrochemical cell, specifically designed for the safe use with radioactive solutions. For U(VI) we observed the complexes UO2(H2O)5(2+), UO2(H2O)4Cl+, UO2(H2O)3Cl2(0), and UO2(H2O)2Cl3- with [Cl-] increasing from 0 to 9 M, and for U(IV) we observed the complexes U(H2O)9(4+), U(H2O)8Cl3+, U(H2O)(6-7)Cl2(2+), and U(H2O)5Cl3+. The distances in the U(VI) coordination sphere are U-Oax = 1.76+/-0.02 A, Oeq = 2.41 +/- 0.02 A, and U-Cl = 2.71 +/- 0.02 A; the distances in the U(IV) coordination sphere are U-O = 2.41 +/- 0.02 A and U-Cl = 2.71 +/- 0.02 A.

Zinc speciation in a smelter-contaminated soil profile using bulk and microspectroscopic techniques.

A soil profile contaminated as a result of Zn smelting operations from the historic Palmerton, PA smelting facility was characterized using X-ray absorption fine structure spectroscopy (XAFS) and X-ray diffraction (XRD) as bulk techniques, coupled with electron microprobe (EM), and microfocused XAFS as microscopic techniques to determine the chemical forms of Zn and elucidate its geochemical fate. The black, organic matter-rich topsoil contained 6200 mg/ kg Zn and was strongly acidic (pH 3.2). Bulk XAFS revealed that about 2/3 of Zn was bound in franklinite and 1/3 bound in sphalerite. Both minerals may have been aerially deposited from the smelter operation. Microspectroscopy detected also minor amounts of Zn adsorbed to Fe and Mn (hydr)oxides as inner-sphere sorption complexes, which may have formed after weathering of the Zn minerals. About 10% of the total Zn in this sample could be easily leached. In contrast, the yellowish, loamy subsoil contained less Zn (890 mg/kg) and had a higher pH of 3.9. XAFS revealed that Zn was mostly bound to Al-groups and to a lesser extent to Fe and Mn (hydr)oxides. Minor amounts of outer-sphere complexes or organic matter-bound Zn species could also be detected. About 70% of the total Zn content could be easily leached, indicating that outersphere sorption complexes have been underestimated and/ or inner-sphere sorption complexes are weak due to the low pH. The Zn forms in the subsoil most likely derive from weathering of the Zn minerals in the topsoil. Due to the lack of minerals incorporating Zn and due to the low pH, the availability of Zn in the subsoil is as high as in the topsoil, while the total concentration is almost 1 order of magnitude smaller.

Ni phases formed in cement and cement systems under highly alkaline conditions: an XAFS study.

X-ray absorption fine structure (XAFS) spectroscopy was applied to assess the solubility-limiting phase of Ni in cement and cement minerals. The study reveals the formation Ni and Al containing hydrotalcite-like layered double hydroxides (Ni-Al LDHs) when cement material (a complex mixture of CaO, SiO2, Al2O3, Fe2O3 and SO3) was treated with Ni in artificial cement pore water under highly alkaline conditions (pH = 13.3). This finding indicates that Ni-Al LDHs and not Ni-hydroxides determine the solubility of Ni in cement materials.

Kinetic controls on Cu and Pb sorption by ferrihydrite.

Metal partitioning in ferrihydrite suspensions may reach equilibrium only after a long reaction time. To determine key factors controlling the kinetics, we measured Cu and Pb uptake as a function of ferrihydrite morphology, reaction temperature, metal competition, and fulvic acid concentration over a period of 2 months. X-ray microscopy, which was used to probe ferrihydrite morphology in suspension, showed that drying irreversibly converted the gellike structure of fresh precipitate into dense aggregates. These dense aggregates sorbed Cu and Pb much slower than the gel. Temperature had a more pronounced effect on the kinetics of metal uptake by ferrihydrite gel than by dense ferrihydrite. Independently of treatment and time, Cu and Pb were bound to the ferrihydrite surface byformation of edge-sharing inner-sphere sorption complexes as confirmed by X-ray absorption fine-structure (XAFS) spectroscopy. This invariable binding mechanism, together with the observed effects of morphology and temperature, are in line with surface diffusion limiting the slow sorption process. The quantification of diffusion-limited surface sites in soils and sediments and the subsequent estimation of the effect of reaction time and temperature will be a challenge for properly predicting the fate of metals in the environment.