Jakob Drebert

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 to the formation of negatively charged Np(V)-carbonate complexes. By increasing pCO2 from 10−3.5 to 10−2.3 atm, the sorption edge is shifted ≈0.5 units to lower pH values. Under anaerobic conditions stronger sorption of 8×10−6 M Np(V) was found, possibly due to partial reduction of Np(V) to Np(IV). The sorption of 8×10−6 M Np(V) under aerobic conditions at pH 8.2 in saturated calcite solution increases continuously with increasing solid-to-liquid ratio of OPA in the range of 2–20 g/L with a constant Kd value of 126±13 L/kg. The sorption isotherm was measured over seven orders of magnitude in Np(V) concentration using 239Np as tracer. The sorption isotherm could be divided in a part of linear sorption behaviour between 10−13–10−9 M Np(V) and non-linear behaviour in the range of 10−9–10−4 M Np(V).

Application of XAFS Spectroscopy to Actinide Environmental Science

The use of XAFS Spectroscopy and related synchrotron radiation techniques for the molecular‐level speciation of environmental contaminants including actinides has led to an improved understanding of the fundamental chemical and biological processes determining their behavior in complex systems. Several recent applications of XAFS spectroscopy to actinides in model systems and more complex environmental samples are reviewed to highlight the impact these studies have on our knowledge about the bioavailability of actinides, the development of remediation strategies, and predictive models for risk assessment. XAFS studies of actinide ion sorption at solid/aqueous solution interfaces are presented in greater detail. Representative examples include XAFS studies in combination with batch‐type experiments of U(VI), Np(V), Pu(III), and Pu(IV) sorption on kaolinite.

Speciation of Np(V) uptake by Opalinus Clay using synchrotron microbeam techniques

Synchrotron-based X-ray absorption spectroscopy has been used to determine the chemical speciation of Np sorbed on Opalinus Clay (OPA, Mont Terri, Switzerland), a natural argillaceous rock revealing a micro-scale heterogeneity. Different sorption and diffusion samples with Np(V) were prepared for spatially resolved molecular-level investigations. Thin sections of OPA contacted with Np(V) solution under aerobic and anaerobic conditions as well as a diffusion sample were analysed spatially resolved. Micro-X-ray fluorescence (μ-XRF) mapping has been used to determine the elemental distributions of Np, Fe and Ca. Regions of high Np concentration were subsequently investigated by micro-X-ray absorption fine structure spectroscopy to determine the oxidation state of Np. Further, micro-X-ray diffraction (μ-XRD) was employed to gain knowledge about reactive crystalline mineral phases in the vicinity of Np enrichments. One thin section was also analysed by electron microprobe to determine the elemental distributions of the lighter elements (especially Si and Al), which represent the main elements of OPA. The results show that in most samples, Np spots with considerable amounts of Np(IV) could be found even when the experiments were carried out in air. In some cases, almost pure Np(IV) LIII-edge X-ray absorption near-edge structure spectra were recorded. In the case of the anaerobic sample, the μ-XRF mapping showed a clear correlation between Np and Fe, indicating that the reduction of Np(V) is caused by an iron(II)-containing mineral which could be identified by μ-XRD as pyrite. These spatially resolved investigations were complemented by extended X-ray absorption fine structure measurements of powder samples from batch experiments under aerobic and anaerobic conditions to determine the structural parameters of the near-neighbour environment of sorbed Np.

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 interface with increased Np concentrations as determined by μ-XRF. Several of these spots are correlated with areas of increased Fe concentration. Np L3-edge μ-XANES spectra revealed that up to 85% of the initial Np(V) was reduced to Np(IV). Pyrite could be identified by μ-XRD as a redox-active mineral phase responsible for the formation of Np(IV). The analysis of the diffusion profile within the clay matrix after an in-diffusion experiment for two months showed that Np(V) is progressively reduced with diffusion distance, i.e. Np(IV) amounted to ≈12% and ≈26% at 30 μm and 525 μm, respectively.

Influence of humic acid on neptunium(V) sorption and diffusion in Opalinus Clay

Summary The influence of 14C-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 both cases and provided comparable distribution coefficients (presence of HA: Kd = 22-32 L/kg, absence of HA: Kd = 30-46 L/kg). As it is known that the interactions of humic substances with actinides depend on various experimental parameters, the effect of HA on Np(V) sorption on 15 g/L OPA was also investigated as a function of pH (6-10) and initial Np concentration (8 μM and 7 pM). A saturated calcite solution was used as a background electrolyte in this case to prevent any dissolution of calcite contained in OPA at low pH. The results showed that the presence of M42 HA increases Np(V) sorption at pH < 7 while lower sorption was obtained above pH 8. Higher sorption at acidic pH can be attributed to strong sorption of HA which increases the number of sorption sites, while sorption decreases at higher pH probably due to formation of soluble ternary neptunium humate carbonate species.

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 material. Spatially resolved X-ray absorption spectroscopy documented a reduction of the highly soluble Pu(V,VI) to the less mobile Pu(IV) within the argillaceous rock material, while bulk investigations showed second-shell scattering contributions, indicating an inner-sphere sorption of Pu on OPA components. Microdiffraction imaging identified the clay mineral kaolinite to play a key role in the immobilization of the reduced Pu. The findings provide strong evidence that reduction and immobilization do not occur as linked processes on a single reactive phase but as decoupled, subsequent, and spatially separated reactions involving different phases of the OPA.

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+ were determined also by out-diffusion experiments. Under ambient condition at pH 7.6, the De value of (1.5 ± 0.1) × 10−11 m2 /s for HTO is lower than that of (1.9 ± 1.1) × 10−11 m2 /s for 22 Na+ , which could be explained by the electrostatic attraction between the negative surface charge of OPA and the sodium cations. For the non-sorbing species HTO, α was 0.15 ± 0.01. For the weakly sorbing species 22 Na+ , α was 0.50 ± 0.02 and Kd equaled (1.5 ± 0.3) × 10−4 m3 /kg. The obtained diffusion parameters for HTO and 22 Na+ in OPA are in good agreement with previous results by Van Loon et al. [1, 2]. FDP developed in this study has been used successfully to determine the parameters De and α for the diffusion of 237 Np(V) in OPA [3].Copyright