0000000000122035
AUTHOR
J. Drebert
The performance of thin layers produced by molecular plating as α-particle sources
Abstract Sources for α-spectroscopy studies were prepared. Constant current density molecular plating was used to produce layers containing the α-particle emitter 147 Sm. Different parameters of the molecular plating process were varied, namely the plating solvent (an isopropanol/isobutanol mixture, pyridine, and N , N -dimethylformamide), the applied deposition time (90, 180, and 360 min), and the surface roughness of the deposition substrate (ca. 10, 20, and 300 nm). Using different analytical techniques, Sm deposition yields, chemical composition of the produced surfaces, surface homogeneity, roughness and morphology were investigated. Alpha spectra were recorded with a Si solid-state de…
Determination of Diffusion Parameters by a Computer Code (FDP) Based on Mathematica 6.0
A computer code named Fitting for Diffusion Parameters (FDP) based on Mathematica 6.0 has been developed for modeling through- and out-diffusion experiments. FDP was used to determine the diffusion coefficients (De ) and the rock capacity factors (α) for tritiated water (HTO) and 22 Na+ and the distribution coefficient (Kd ) of 22 Na+ in Opalinus Clay (OPA). The values for De and α were obtained by fitting the results of experimental data of both transient and steady-state phases to the analytical solution of accumulated activity. The quality of the parameters De and α was tested by using them as input parameters in the equation of flux. Moreover, the diffusion parameters of HTO and 22 Na+ …
Structural characterization of U(VI) surface complexes on kaolinite in the presence of humic acid using EXAFS spectroscopy.
To determine the influence of humic acid (HA), pH, and presence of atmospheric CO2 on the sorption of U(VI) onto kaolinite, the structure of the surface complexes was studied by U L III-edge extended X-ray absorption fine structure (EXAFS) spectroscopy. The best fits to the experimental EXAFS data were obtained by including two uranium coordination shells with two axial (O ax) and five equatorial (O eq) oxygen atoms at 1.77+/-0.02 and 2.34+/-0.02 A, respectively, and two coordination shells with one Al/Si atom each at 3.1 and 3.3 A. As in the case of the binary system U(VI)-kaolinite, uranium forms inner-sphere surface complexes by edge sharing with aluminum octahedra and/or silicon tetrahe…
Sorption of neptunium(V) on Opalinus Clay under aerobic/anaerobic conditions
Abstract The interaction between neptunium(V) and a natural argillaceous rock (Opalinus Clay (OPA), Mont Terri, Switzerland) has been investigated in batch sorption experiments by varying pH (6–10), Np(V) concentration (10−12–10−4 M), solid-to-liquid ratio (2–20 g/L), and partial pressure of CO2 (10−3.5 and 10−2.3 atm) under aerobic/anaerobic conditions in saturated calcite solution. All batch experiments were carried out using well characterized aerobic and anaerobic dry powders of OPA. The results show a great influence of pH on Np(V) sorption. Under aerobic conditions sorption increases with increasing pH until maximum sorption is reached between pH 8–9. At pH>9 sorption decreases due…
Geochemical Interactions of Plutonium with Opalinus Clay Studied by Spatially Resolved Synchrotron Radiation Techniques
Plutonium plays an important role within nuclear waste materials because of its long half-life and high radiotoxicity. The aim of this study was to investigate with high spatial resolution the reactivity of the more oxidized forms of Pu(V,VI) within Opalinus Clay (OPA) rock, a heterogeneous, natural argillaceous rock considered as a potential repository host. A combination of synchrotron based X-ray microprobe and bulk techniques was used to study the spatial distribution and molecular speciation of Pu within OPA after diffusion and sorption processes. Microscopic chemical images revealed a pronounced impact of geochemical heterogeneities concerning the reactivity of the natural barrier mat…
Neptunium(V) Sorption and Diffusion in Opalinus Clay
The sorption and diffusion behavior of 8 x 10(-6) M Np(V) in Opalinus Clay (OPA) with synthetic pore water (pH 7.6) as mobile phase was studied under ambient conditions by batch and diffusion experiments, respectively. The Kd value determined by batch experiments with OPA suspensions is equal to 0.025 +/- 0.005 m3/kg. The diffusion-accessible porosity epsilon of intact OPA as determined by through- and out-diffusion experiments with tritiated water (HTO) is equal to 0.15 +/- 0.01. The diffusion coefficient De and the rock capacity factor alpha of 22Na+ in OPA were measured by through-, out-, and in-diffusion experiments and asserted the reliability of these diffusion techniques. For the dif…
Influence of humic acid on neptunium(V) sorption and diffusion in Opalinus Clay
SummaryThe influence of14C-labeled M42 humic acid (HA) on the interaction between neptunium(V) and natural clay rock (Opalinus Clay (OPA), Switzerland) has been investigated in batch sorption and diffusion experiments under ambient air conditions. The effect of 10 mg/L HA on the diffusion of 8 μM Np(V) in OPA has been investigated in synthetic OPA pore water (pH 7.6, I = 0.4M) for the first time. Batch sorption experiments as a function of solid-to-liquid ratio (4-20 g/L) were performed under same experimental conditions to compare distribution coefficients obtained from both diffusion and sorption experiments. These experiments showed only a slight influence of HA on Np(V) uptake by OPA in…
Smooth crack-free targets for nuclear applications produced by molecular plating
The production process of smooth and crack-free targets by means of constant current electrolysis in organic media, commonly known as molecular plating, was optimized. Using a Nd salt, i.e., [Nd(NO3)(3)center dot 6H(2)O], as model electrolyte several constant current density electrolysis experiments were carried out to investigate the effects of different parameters, namely the plating solvent (isopropanol and isobutanol mixed together, pyridine, and N,N-dimethylformamide), the electrolyte concentration (0.11, 0.22, 0.44 mM), the applied current density (0.17, 0.3, 0.7, and 1.3 mA/cm(2)), and the surface roughness of the deposition substrates (12 and 24 nm). Different environments (air and …
Influence of temperature and background electrolyte on the sorption of neptunium(V) on Opalinus Clay
Abstract The temperature dependence of the sorption of 8 μM neptunium(V) on Opalinus Clay (OPA, Mont Terri, Switzerland) was investigated between 40 and 80 °C and compared to previous results for 20 °C. The batch experiments were performed under ambient air conditions in synthetic pore water (pH = 7.6, I = 0.4 M) under variation of the solid-to-liquid ratio between 2 and 20 g/L. Under these conditions the sorption of Np(V) on OPA was found to be an endothermic process as the average distribution coefficient (K d ) increases continuously with increasing temperature from 23 ± 4 L/kg at 40 °C to 678 ± 254 L/kg at 80 °C. In the temperature range of 40-80 °C, the plot of log(K d ) vs. 1/T could …
Elucidation of constant current density molecular plating
Abstract The production of thin layers by means of constant current or constant voltage electrolysis in organic media is commonly known as molecular plating. Despite the fact that this method has been applied for decades and is known to be among the most efficient ones for obtaining quantitative deposition, a full elucidation of the molecular plating is still lacking. In order to get a general understanding of the process and hence set the basis for further improvements of the method, constant current density electrolysis experiments were carried out in a mixture of isopropanol and isobutanol containing millimolar amounts of HNO 3 together with [Nd(NO 3 ) 3 ·6H 2 O] used as a model electrol…
Speciation of neptunium during sorption and diffusion in natural clay
In argillaceous rocks, which are considered as a potential host rock for nuclear waste repositories, sorption and diffusion processes govern the migration behaviour of actinides like neptunium. For the safety analysis of such a repository, a molecular-level understanding of the transport and retardation phenomena of radioactive contaminants in the host rock is mandatory. The speciation of Np during sorption and diffusion in Opalinus Clay was studied at near neutral pH using a combination of spatially resolved synchrotron radiation techniques. During the sorption and diffusion experiments, the interaction of 8 μM Np(V) solutions with the clay lead to the formation of spots at the clay-water …