Melissa A. Denecke

ROBL – a CRG beamline for radiochemistry and materials research at the ESRF

The paper describes the Rossendorf beamline (ROBL) built by the Forschungszentrum Rossendorf at the ESRF. ROBL comprises two different and independently operating experimental stations: a radiochemistry laboratory for X-ray absorption spectroscopy of non-sealed radioactive samples and a general purpose materials research station for X-ray diffraction and reflectometry mainly of thin films and interfaces modified by ion beam techniques.

Structure and reactivity of the calcite-water interface

The zetapotential of calcite in contact with aqueous solutions of varying composition is determined for pre-equilibrated suspensions by means of electrophoretic measurements and for non-equilibrium solutions by means of streaming potential measurements. Carbonate and calcium are identified as charge determining ions. Studies of the equilibrium solutions show a shift of isoelectric point with changing CO(2) partial pressure. Changes in pH have only a weak effect in non-equilibrium solutions. The surface structure of (104)-faces of single crystal calcite in contact to solutions corresponding to those of the zetapotential investigations is determined from surface diffraction measurements. The results reveal no direct indication of calcium or carbonate inner-sphere surface species. The surface ions are found to relax only slightly from their bulk positions; the most significant relaxation is a ∼4° tilt of the surface carbonate ions towards the surface. Two ordered layers of water molecules are identified, the first at 2.35±0.05Å above surface calcium ions and the second layer at 3.24±0.06Å above the surface associated with surface carbonate ions. A Basic-Stern surface complexation model is developed to model observed zetapotentials, while only considering outer-sphere complexes of ions other than protons and hydroxide. The Basic-Stern SCM successfully reproduces the zetapotential data and gives reasonable values for the inner Helmholtz capacitance, which are in line with the Stern layer thickness estimated from surface diffraction results.

An EXAFS and TRLFS study of the sorption of trivalent actinides onto smectite and kaolinite

Summary The structure parameters of the Am3+ aquo ion and of Am(III) sorbed onto smectite and kaolinite at varying pH are analyzed using EXAFS. An Am-O distance of 2.47-2.49Å is found and a coordination number of 8-9 oxygen atoms is observed for the Am3+ and its hydration sphere. Combined TRLFS (Cm(III)) and EXAFS (Am(III)) results show that An(III) sorbs onto smectite at pH 4, forming an outer-sphere complex and retains its complete primary hydration sphere. With increasing pH, inner-sphere sorption onto smectite and kaolinite occurs. The overall number of oxygen atoms coordinating the actinide ion remains about the same at pH 6, with four water molecules being replaced by oxygen atoms from the mineral surface during inner-sphere complex formation. The coordination number of sorbed Am(III) at pH 8 exhibits an apparent decrease, which may be affected by the formation of ternary OH-/Am/clay mineral surface species.

Solubility of amorphous Th(IV) hydroxide - application of LIBD to determine the solubility product and EXAFS for aqueous speciation

Summary The solubility of amorphous Th(IV) hydroxide at pH 3.0–13.5 and the aqueous speciation at pH < 4 are investigated in 0.5 M NaCl and 25 °C. The laser-induced breakdown detection (LIBD) is used to monitor the initial formation of thorium hydroxide colloids during the coulometric titration of 1.2×10−2−1.0×10−5 M thorium solutions in the pH range of 2.7–4.5. The accurate solubility limit determined by this method is comparable with data measured from undersaturation with an X-ray amorphous solid precipitated at higher pH and dried at room temperature. Based on hydrolysis constants selected from the literature, the solubility product of Th(OH)4(am) in 0.5 M NaCl is calculated to be log K′sp = −44.48 ± 0.24 and log K°sp = −47.8 ± 0.3 (converted to I=0 with the SIT coefficients of the NEA-TDB). In other solubility studies with amorphous Th(IV) hydroxide or hydrous oxide, considerably higher thorium concentrations are measured at pH 3.5–5. Therefore, solutions of comparable H+ and thorium concentrations are prepared by careful coulometric titration and examined by ultrafiltration, LIBD and X-ray absorption fine structure (XAFS) spectroscopy. These measurements demonstrate the presence of a large amount of small Th(IV) colloids. The ThL3 edge EXAFS spectra of these colloidal suspensions are similar to that of the amorphous solid.

The structure of U (super 6+) sorption complexes on vermiculite and hydrobiotite

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.

Technetium Speciation in Cement Waste Forms Determined by X-ray Absorption Fine Structure Spectroscopy

The chemistry of technetium in cement waste forms has been studied with X-ray absorption fine structure (XAFS) spectroscopy. Using the Tc /f-edge X-ray absorption near-edge structure (XANES) as a probe of the technetium speciation, our results show that partial reduction of the pertechnetate ion, TcOj, takes place in the presence of the cement additive, blast fumace slag (BFS). The addition of the reducing agents FeS, NazS, and NaHjPOz produces more extensive reduction of TcOl, while the Compounds FeO, Fe304, and MnjOi are observed to be unreactive. The extended X-ray absorption fine structure (EXAFS) data for the BFS, Na^S, and FeS treated cements indicate the presence of Tc Clusters possessing first shell S coordination. For the Na2S and FeS additives, Tc-Tc interactions are detected in the EXAFS demonstrating an extended structure similar to that of TcSa. The EXAFS spectrum of the NaHzPOj treated cement reveals T c O and Tc-Tc interactions that resemble those found in the structure of TcO,.

CHARACTERIZATION OF HYDROUS URANYL SILICATE BY EXAFS

Extended X-ray absorption fine structure (EXAFS) analysis was performed on uranyl orthosilicate, (U02)2Si04 · 2H20, and uranium(VI) sorbed onto silicic acid and silica gel. Uranyl orthosilicate was investigated as a reference for EXAFS studies of similar but non-crystalline uranium, oxygen, and silicon containing samples. Fitting the EXAFS spectrum yields the following distances for the first four coordination shells of uranium: U— Oax = 1.79 Á, U-O e i l = 2.38 λ , U S i = 3.16 Â, and U U = 3.88 A. These values agree well with results from single-crystal X-ray diffraction (XRD) measurements. Structural parameters of light elements such as oxygen and silicon at distances greater than 3.5 A could not be detected without a priori knowledge of their presence. The EXAFS spectra of uranyl species sorbed at pH 4 onto silicic acid and silica gel are identical indicating similar uranyl coordination. The main characteristic of the surface species are two well-separated oxygen coordination shells in the equatorial uranyl plane at 2.27 and 2.50 A. The results of the EXAFS analysis favor the interpretation of the uranyl surface species as an inner-sphere, mononuclear, bidentate complex.

Geomicrobiological Redox Cycling of the Transuranic Element Neptunium

Microbial processes can affect the environmental behavior of redox sensitive radionuclides, and understanding these reactions is essential for the safe management of radioactive wastes. Neptunium, an alpha-emitting transuranic element, is of particular importance because of its long half-life, high radiotoxicity, and relatively high solubility as Np(V)O(2)(+) under oxic conditions. Here, we describe experiments to explore the biogeochemistry of Np where Np(V) was added to oxic sediment microcosms with indigenous microorganisms and anaerobically incubated. Enhanced Np removal to sediments occurred during microbially mediated metal reduction, and X-ray absorption spectroscopy showed this was due to reduction to poorly soluble Np(IV) on solids. In subsequent reoxidation experiments, sediment-associated Np(IV) was somewhat resistant to oxidative remobilization. These results demonstrate the influence of microbial processes on Np solubility and highlight the critical importance of radionuclide biogeochemistry in nuclear legacy management.

MEASUREMENTS OF THE STRUCTURAL PARAMETERS FOR THE INTERACTION OF URANIUM(VI) WITH NATURAL AND SYNTHETIC HUMIC ACIDS USING EXAFS

Fluka humic acid having 87, 35, 10, and 8 percent of its proton exchange capacity, % PEC, loaded with uranyl ions and synthetic humic acid loaded with 14% PEC were prepared either from solution or from suspension. The interaction of uranium with the humic acids was studied using U L„ redge extended X-ray absorption fine structure, EXAFS, and infrared, IR, spectroscopy. IR results indicate complexation of the uranyl ions onto the humic acid carboxylic groups. The uranium—oxygen (U—O) bond distances determined from the EXAFS analysis are the same, within the experimental error, for both synthetic and natural uranyl humates, for samples with large loadings and samples with relatively low uranyl loadings, as well as for dry and wet paste samples. In all samples studied, axial U—Ο distances of 1.77-1.78 A and five equatorial oxygen atoms at distances of 2.37—2.39 A were found. Comparison of the equatorial bond distances to those for various uranyl carboxylates reported in the literature indicates that the humic acid carboxylate groups act predominantly as monodentate ligands when bound to the uranyl unit. Additional, neutral ligands must also be coordinated to the uranyl ion in order to satisfy the uranyl cation coordination number determined as five.

The INE-Beamline for actinide science at ANKA

Since its inauguration in 2005, the INE-Beamline for actinide research at the synchrotron source ANKA (KIT North Campus) provides dedicated instrumentation for x-ray spectroscopic characterization of actinide samples and other radioactive materials. R&D work at the beamline focuses on various aspects of nuclear waste disposal within INEs mission to provide the scientific basis for assessing long-term safety of a final nuclear waste repository. The INE-Beamline is accessible for the actinide and radiochemistry community through the ANKA proposal system and the European Union Integrated Infrastructure Initiative ACTINET-I3. Experiments with activities up to 1 × 10(+6) times the European exemption limit are feasible within a safe but flexible containment concept. Measurements with monochromatic radiation are performed at photon energies varying between ~2.1 keV (P K-edge) and ~25 keV (Pd K-edge), including the lanthanide L-edges and the actinide M- and L3-edges up to Cf. The close proximity of the INE-Beamline to INE controlled area labs offers infrastructure unique in Europe for the spectroscopic and microscopic characterization of actinide samples. The modular beamline design enables sufficient flexibility to adapt sample environments and detection systems to many scientific questions. The well-established bulk techniques x-ray absorption fine structure (XAFS) spectroscopy in transmission and fluorescence mode have been augmented by advanced methods using a microfocused beam, including (confocal) XAFS/x-ray fluorescence detection and a combination of (micro-)XAFS and (micro-)x-ray diffraction. Additional instrumentation for high energy-resolution x-ray emission spectroscopy has been successfully developed and tested.