Band 93, Heft 1 -

In preparation for the experimental investigation of chemical properties of element 112 model studies were conducted based on the assumed similarity of element 112 to either the noble gas Rn or the transition metal Hg, its supposed lighter homologue in group 12. The adsorption behavior of elemental Hg on the transition metals Ag, Au, Ni, Pd, and Pt were investigated experimentally by off-line gas thermochromatography. The deduced adsorption data of Hg were compared with new values calculated using the Eichler–Miedema model. The observed sequence of increasing Hg-metal-interactions for Ag < Ni < Au < Pd < Pt confirms the predicted trend. The only exception was Pd, on which Hg was calculated to adsorb at a higher temperature than on Pt. Difficulties to obtain reproducible clean surfaces of Ag, Ni, Pd, and Pt led to the choice of Au as the best metal surface suitable to adsorb Hg. For fast on-line gas thermochromatography studies on metallic surfaces a new set-up was developed based on the In-situ Volatilization and On-line detection technique (IVO). This set-up was tested in on-line thermochromatographic investigations with short-lived Hg isotopes and 219 Rn, using Au or Pd as stationary surfaces. An overall efficiency of about 60% and a transportation time less than 25 s was determined for this newly designed IVO. A separation factor of more than 10 6 was estimated for non-volatile species.

The separation of Am(III) and Cm(III) by countercurrent chromatography (CCC) was achieved using the liquid phase systems "diamide–hydrogenated tetrapropylene (TPH)–HNO 3 " following the optimisation of: (i) the compositions of the mobile (HNO 3 concentration) and the stationary (nature of the diamide and its concentration in TPH) phases, (ii) column length and (iii) operating parameters of the CCC (flow rate of the mobile phase and rotation speed of the coil column). The following diamide extractants have been studied: (i) N,N´-dimethyl-N,N´-dibutyltetradecylmalonamide (DMDBTDMA), (ii) N,N´-dimethyl-N,N´-dioctylhexyl-ethoxymalonamide (DMDOHEMA) and (iii) N,N´-dimethyl-N,N´-dibutyldodecylethoxymalonamide (DMDBDDEMA). It is shown that these diamides can be used for the separation of Am(III) and Cm(III) by CCC. Increasing the column length leads to an increase of the stationary phase retention on the column while improving the Am/Cm separation. Increasing the speed of rotation of the centrifuge from 660 to 950 rpm also results in increasing the stationary phase retention but does not influence the resolution of the Am/Cm separation. Decreasing the flow rate of the mobile phase from 1.0 to 0.5 mL/min leads to a better resolution of Am and Cm separation. The best Am/Cm separation was achieved with systems based on DMDBDDEMA and DMDOHEMA in TPH using a two-layer coil column and an isocratic elution mode. The application of CCC makes it possible to separate the elements within 100 min: the Cm fraction contains 99.5% of Cm(III) and 0.6% of Am(III) inventories and the Am fraction contains 99.4% of Am(III) and 0.5% of Cm(III).

The structure of Np(V) humic acid (HA) complexes at pH 7 was studied by extended X-ray absorption fine structure analysis (EXAFS). For the first time, the influence of phenolic OH groups on the complexation of HA and Np(V) in the neutral pH range was investigated using modified HAs with blocked phenolic OH groups and Bio-Rex70, a cation exchange resin having only carboxyl groups as proton exchanging sites. The formation of Np(V) humate complexes was verified by near-infrared (NIR) spectroscopy. Axial Np-O bond distances of 1.84–1.85 Å were determined for the studied Np(V) humate complexes and the Np(V)-Bio-Rex70 sorbate. In the equatorial plane Np(V) is surrounded by about 3 oxygen atoms with bond lengths of 2.48–2.49 Å. The comparison of the structural parameters of the Np(V) humates with those of Np(V)-Bio-Rex70 points to the fact that the interaction between HA and Np(V) in the neutral pH range is dominated by carboxylate groups. However, up to now a contribution of phenolic OH groups to the interaction process cannot be excluded completely. The comparison of the obtained structural data for the Np(V) humates to those of Np(V) carboxylates and Np(V) aquo ions reported in the literature indicates that humic acid carboxylate groups predominantly act as monodentate ligands. A differentiation between equatorial coordinated carboxylate groups and water molecules using EXAFS spectroscopy is impossible.

The hydrolysis constants and the solubility products of the oxide/hydroxides of Pa(IV) and Pa(V) have been first reviewed and re-evaluated through the application of three comparative methods: the simple Hard Sphere Electrostatic model (HSE), the Brown and Wanner Theory (BWT) and the Correlation between Solubility and Complex stability constants of a metal ion (CSC). The latter method is the most empirical one, but it gives coherent results, in agreement with the few published experimental values, for all the possible aqua species of protactinium (Pa 4+ , Pa 5+ , PaO 2 + and PaO 3+ ). The selected thermodynamic data have then been used to predict the protactinium solubility in non complexing media of various pH and redox potential.

The option of direct disposal of spent nuclear fuel in a deep geological formation raises the need to investigate the long-term behavior of the UO 2 matrix in aqueous media subjected to α-β-γ radiation. The β-γ emitters account for most of the activity of spent fuel at the moment it is removed from the reactor, but diminish within a millennial time frame by over three orders of magnitude to less than the long-term activity. The latter persists over much longer time periods and must therefore be taken into account over a geological disposal time scale. Leaching experiments with solution renewal were carried out on UO 2 pellets doped with alpha emitters ( 238 Pu and 239 Pu) to quantify the impact of alpha irradiation on UO 2 matrix alteration. Three batches of doped UO 2 pellets with different alpha flux levels (3.30×10 4 , 3.30×10 5 , and 3.2×10 6 α cm -2 s -1 ) were studied. The results obtained in aerated and deaerated media immediately after sample annealing or interim storage in air provide a better understanding of the UO 2 matrix alteration mechanisms under alpha irradiation. Interim storage in air of UO 2 pellets doped with alpha emitters results in variations of the UO 2 surface reactivity, which depends on the alpha particle flux at the interface and on the interim storage duration. The variation in the surface reactivity and the greater uranium release following interim storage cannot be attributed to the effect of alpha radiolysis in aerated media since the uranium release tends toward the same value after several leaching cycles for the doped UO 2 pellet batches and spent fuel. Oxygen diffusion enhanced by alpha irradiation of the extreme surface layer and/or radiolysis of the air could account for the oxidation of the surface UO 2 to UO 2+x . However, leaching experiments performed in deaerated media after annealing the samples and preleaching the surface suggest that alpha radiolysis does indeed affect the dissolution, which varies with the flux at the UO 2 /water interface.

The complexation of redox sensitive elements by humic acid (HA), described through the charge neutralisation model (CNM), has been reviewed in order to have a comprehensive scope. The data acquired in HUMICS program on thorium(IV), and data available in the literature, were reinterpreted according to the CNM, and adapted to uranium(IV), neptunium(IV) and plutonium(IV) through analogy in order to draw a boundary prediction. Otherwise, available data obtained in the framework of the CNM were used, or adapted if necessary, for other redox states when the analogy is justified, i.e. Am 3+ -Cm 3+ for Pu 3+ , NpO 2 + for PuO 2 + and UO 2 2+ for PuO 2 2+ . The obtained speciation diagrams indicate that, when (HA)=100 mg/L, redox sensitive actinides should be reduced to their +IV state when E h ≤650 mV/SHE for plutonium, E h ≤100 mV/SHE for neptunium and E h ≤-20 mV/SHE for U. Plutonium could be present as mixtures of plutonium(III) and (IV) depending on the pH value in reducing ground waters -150 ≤ E h (mV/SHE) ≤ 150. The known reduction of neptunium(V) to neptunium(IV) in Gorleben ground waters seems also well represented, so is the stability of uranium(VI) in humic solution when E h ≥ 100 mV/SHE. Conversely, the known association of plutonium(VI) in marine systems is not satisfactorily represented, so does is the uranium behaviour under reducing conditions. Experiments under well-controlled conditions are still needed to ascertain the plutonium and uranium comportment in the presence of humic acid.

A series of batch sorption and column experiments was conducted to investigate sorption and transport behavior of 99 Tc, 129 I, 79 Se, and 90 Sr on and through borehole sediments collected from the proposed low-level radioactive waste disposal facility at the Hanford Site (200 East Area). Batch sorption experiments were conducted on Hanford sediment using uncontaminated Hanford groundwater and simulated glass leachates spiked with individual radionuclides. Strongest sorption occurred for 90 Sr, while 79 Se sorption was intermediate, and 129 I and 99 Tc showed the least sorption affinities on Hanford sediment among these radionuclides studied. The results of column experiments that measured transport behavior of these radionuclides through Hanford sediment were similar to the mobility that can be calculated from the batch sorption results, that is high mobility for 99 Tc and 129 I compared to the intermediate and strong retardation for 79 Se and 90 Sr, respectively. These contaminant sorption data on sediments from below the proposed disposal facility, especially the tests using simulated glass leachate, corroborate values obtained for sediments collected in the past from near by locations and for generic solutions such as regional groundwater. These new data should provide more technical defensibility for past performance assessment predictions that did not use site-specific sediments and leachates. Further, the new data will be incorporated into future performance assessment activities that will update and improve past predictions.