Tris-{hydridotris(1-pyrazolyl)borato}actinide Complexes: Synthesis, Spectroscopy, Crystal Structure, Bonding Properties and Magnetic Behaviour.

The isostructural compounds of the trivalent actinides uranium, neptunium, plutonium, americium, and curium with the hydridotris(1-pyrazolyl)borato (Tp) ligand An[η3 -HB(N2 C3 H3 )3 ]3 (AnTp3 ) have been obtained through several synthetic routes. Structural, spectroscopic (absorption, infrared, laser fluorescence) and magnetic characterisation of the compounds were performed in combination with crystal field, density functional theory (DFT) and relativistic multiconfigurational calculations. The covalent bonding interactions were analysed in terms of the natural bond orbital (NBO) and quantum theory of atoms in molecules (QTAIM) models.

Interdisciplinary Round-Robin Test on Molecular Spectroscopy of the U(VI) Acetate System.

A comprehensive molecular analysis of a simple aqueous complexing system-U(VI) acetate-selected to be independently investigated by various spectroscopic (vibrational, luminescence, X-ray absorption, and nuclear magnetic resonance spectroscopy) and quantum chemical methods was achieved by an international round-robin test (RRT). Twenty laboratories from six different countries with a focus on actinide or geochemical research participated and contributed to this scientific endeavor. The outcomes of this RRT were considered on two levels of complexity: first, within each technical discipline, conformities as well as discrepancies of the results and their sources were evaluated. The raw data from the different experimental approaches were found to be generally consistent. In particular, for complex setups such as accelerator-based X-ray absorption spectroscopy, the agreement between the raw data was high. By contrast, luminescence spectroscopic data turned out to be strongly related to the chosen acquisition parameters. Second, the potentials and limitations of coupling various spectroscopic and theoretical approaches for the comprehensive study of actinide molecular complexes were assessed. Previous spectroscopic data from the literature were revised and the benchmark data on the U(VI) acetate system provided an unambiguous molecular interpretation based on the correlation of spectroscopic and theoretical results. The multimethodologic approach and the conclusions drawn address not only important aspects of actinide spectroscopy but particularly general aspects of modern molecular analytical chemistry.

Macroscopic and spectroscopic investigations on Eu(III) and Cm(III) sorption onto bayerite (ß-Al(OH)3) and corundum (α-Al2O3).

The interaction of trivalent Cm and Eu with the aluminum hydroxide bayerite (ß-Al(OH)3) and the aluminum oxide corundum (α-Al2O3) was investigated by batch sorption experiments and time resolved laser fluorescence spectroscopy (TRLFS). The experimental methods for both polymorphs show similar pH dependent sorption behavior at trace metal ion concentrations (∼10(-7) M), i.e. similar Eu sorption edges and nearly identical Cm speciation between pH=3 and 13. In this pH range the Cm aquo ion as well as the Cm(III) surface species surface⋯Cm(OH)x(H2O)(5-x) (x=0, 1, 2) can be distinguished by TRLFS. The similar sorption data point to a (surface) transformation of the thermodynamically unstable Al2O3 surface into bayerite, in agreement with the similar isoelectric points obtained for both minerals (pH(IEP)=8.6-8.8). The pH dependent surface charge is most likely due to the protonation/deprotonation of singly coordinated Al-OH surface groups, prevailing on the edge planes of the rod-like bayerite crystals and the surface of the colloidal Al2O3 particles. These surface groups are also believed to act as ligands for lanthanide/actinide(III) surface complexation. In contrast to the similar sorption behavior at trace metal ion concentrations, discrepancies are observed at higher Eu levels. While similar sorption edges occur up to 7×10(-7) M Eu for corundum, the pH edge on bayerite is gradually shifted to higher pH values in this Eu concentration range. The latter behavior may be related either to the existence of multiple sorption sites with different sorption affinities, or to the influence of an additional amorphous Al-phase, forming in the course of the bayerite synthesis.

Actinide geochemistry: from the molecular level to the real system.

Geochemical processes leading to either mobilization or retention of radionuclides in an aquifer system are significantly influenced by their interaction with rock, sediment and colloid surfaces. Therefore, a sound safety assessment of nuclear waste disposal requires the elucidation and quantification of those processes. State-of-the-art analytical techniques as e.g. laser- and X-ray spectroscopy are increasingly applied to study solid-liquid interface reactions to obtain molecular level speciation insight. We have studied the sorption of trivalent lanthanides and actinides onto aluminium oxides, hydroxides and purified clay minerals by the time-resolved laser fluorescence spectroscopy and X-ray-absorption spectroscopy. Chemical constitution and structure of surface bound actinides are proposed based on spectroscopic information. Open questions still remain with regard to the exact nature of mineral surface ligands and the mineral/water interface. Similarities of spectroscopic data obtained for M(III) sorbed onto gamma-alumina, and clay minerals suggest the formation of very comparable inner-sphere surface complexes such as S-O-An(III)(OH)x(2-x)(H2O)5-x at pH > 5. Those speciation data are found consistent with those predicted by surface complexation modelling. The applicability of data obtained for pure mineral phases to actinide sorption onto heterogeneously composed natural clay rock is examined by experiments and by geochemical modelling. Good agreement of experiment and model calculations is found for U(VI) and trivalent actinide/lanthanide sorption to natural clay rock. The agreement of spectroscopy, geochemical modelling and batch experiments with natural rock samples and purified minerals increases the reliability in model predictions. The assessment of colloid borne actinide migration observed in various laboratory and field studies calls for detailed information on actinide-colloid interaction. Kinetic stabilization of colloid bound actinides can be due to inclusion into inorganic colloid matrix or by macromolecular rearrangement in case of organic, humic/fulvic like colloids. Only a combination of spectroscopy, microscopy and classical batch sorption experiments can help to elucidate the actinide-colloid interaction mechanisms and thus contribute to the assessment of colloids for radionuclide migration.

Proton and trivalent metal cation binding by dissolved organic matter in the opalinus clay and the callovo-oxfordian formation.

We investigated the proton and trivalent metal binding of dissolved organic matter (DOM) in in situ pore water and anoxic rock extracts of two potential host rocks for the disposal of radioactive waste, i.e., the Opalinus Clay (OPA) and the Callovo-Oxfordian formation (COx). The proton, curium, and europium binding properties of the OPA pore water and the extracted DOM of both rocks were studied with acid-base titrations, time-resolved laser fluorescence spectroscopy (TRLFS), and voltammetry, respectively. Protons were mostly buffered by inorganic compounds. DOM contributed to the total proton buffering capacity of the samples only to a small extent. Significant complexation of curium by DOM was observed for OPA pore water by TRFLS in contrast to little complexation by DOM detected in the OPA and COx extracts. The data on europium binding in OPA pore water were described by the presence of 14.3 microM organic ligands exhibiting a conditional affinity constant of log beta = 6.50. Calculations of europium speciation under in situ conditions indicated that carbonates largely controlled the speciation of europium in OPA and COx. In the OPA formation, the presence of DOM may enhance the solubility of europium by 5 x 10(-8) M, representing about one-third of total dissolvable europium.

Kinetic investigation of Eu(III)-humate interactions by ion exchange resins.

The kinetic stability of radionuclides bound to aqueous colloids is a determining factor in their migration from a radioactive waste repository. The cation exchangers Chelex-100, Dowex 50Wx4, and Cellphos (cellulose phosphate) have been shown a promising tool for kinetic investigations. This study assesses the applicability of different exchange resins for Eu humate dissociation kinetics investigations. All resins were found to produce satisfactory results. A systematic study of parameters affecting the dissociation rates of Eu(III) humate complexes was performed. A set of purified humic substances was found to behave in the same way. However, unpurified Aldrich humic acid showed significant differences.

Uptake of Cm(III) and Eu(III) by calcium silicate hydrates: a solution chemistry and time-resolved laser fluorescence spectroscopy study.

The interaction of the two chemical homologues [Cm(III) and Eu(III)] with calcium silicate hydrates (CSH phases) at pH 13.3 has been investigated in batch-type sorption studies using Eu(III) and complemented with time-resolved laser fluorescence spectroscopy (TRLFS) using Cm(III). The sorption data for Eu(III) reveal fast sorption kinetics and a strong uptake by CSH phases with distribution ratios of (6 +/- 3) x 10(5) L kg(-1). Three different Cm(III) species have been identified: A nonfluorescing species, which was identified as a curium hydroxide (surface) precipitate, and two fluorescing Cm(III)/CSH-sorbed species. The fluorescing sorbed species have characteristic emission spectra with main peak maxima at 618.9 and 620.9 nm and fluorescence emission lifetimes of 289 +/- 11 and 1482 +/- 200 micros, respectively. From the fluorescence lifetimes, it was calculated that the two fluorescing Cm(III) species have one or two and no water molecules left in their first coordination sphere, suggesting that these species are incorporated into the CSH structure. A structural model for Cm(III) and Eu(III) incorporation into CSH phases is proposed based on the substitution for Ca at two different types of sites in the CSH structure.