U(VI) retention by Ca-bentonite and clay minerals at (hyper)alkaline conditions

Clays are considered as potential host rocks and backfill material for deep geological repositories for radioactive waste. Therefore, profound understanding of radionuclide retention processes at clay mineral surfaces is essential for a long-term safety assessment. This understanding has already been generated in the past for simple chemical systems, in which experiments are easy to conduct and interpretation is straightforward. However, there is still a lack of molecular process understanding when considering complex natural systems (low radionuclide concentrations, high ionic strength, high pH values, multi-mineral solid phases, complex solution composition). This thesis aims to close some of these knowledge gaps, focusing on U(VI) and Np(VI) sorption on clays at (hyper)alkaline conditions. pH values between 10 and 13 can prevail in the near-field of a radioactive waste repository as a result of the degradation of concrete, which is part of the geo-engineered barrier. Existing studies on radionuclide sorption on clays do not exceed pH 10. Therefore, within this work, a comprehensive investigation in the pH range 8-13 was conducted. This included the quantification of radionuclide retention in batch sorption experiments as well as spectroscopic investigations to generate understanding about the underlying retention mechanisms on a molecular level. Beside the pH, additional focus was on the influence of dissolved carbonate and calcium on radionuclide sorption at (hyper)alkaline conditions. Next to two small chapters dealing with the stability and surface charge of Ca-bentonite at (hyper)alkaline conditions (chapter 4.1) and the influence of ISA on U(VI) sorption at high pH values (chapter 4.3), the thesis can be subdivided in two major parts. The first part (chapter 4.2) is a detailed investigation of U(VI) sorption on Ca-bentonite at (hyper)alkaline conditions in mixed electrolyte solutions. Batch sorption experiments were conducted, varying a number of experimental parameters (sorption time, S/L ratio, U(VI) concentration, pH value, carbonate concentration) and assessing their effect on U(VI) sorption. In order to be able to explain the observed sorption behavior, next to U(VI) solubility tests, spectroscopic techniques were applied. The aqueous speciation of U(VI) was investigated with TRLFS, while its surface speciation was probed with ATR FT-IR, site-selective TRLFS, EXAFS and CTR/RAXR. Since the results of this chapter indicated a great importance of the presence of calcium (see below), the second major part of the thesis (chapter 4.4) was dedicated to a careful evaluation of the influence of calcium on An(VI) sorption on clay minerals at (hyper)alkaline conditions. This encompasses the sorption of Ca(II) on Ca-bentonite and its effect on the bentonite surface charge. Furthermore, U(VI) batch sorption experiments with Na-montmorillonite, synthetic kaolinite and muscovite were conducted in 0.1 M NaCl as well as in 0.1 M NaCl + 0.02 M CaCl2 at pH 8-13, in order to quantify the influence of calcium on U(VI) sorption on supposedly Ca-free mineral phases. Site-selective TRLFS was applied with the aim to observe U(VI) sorption species involving calcium. Finally, complementary sorption experiments Np(VI) on muscovite were performed in order to check whether its sorption behavior is analogous to U(VI) under the given conditions. Batch sorption experiments demonstrate that U(VI) retention on Ca-bentonite can be very effective at pH > 10, even in the presence of carbonate and despite the prevalence of anionic aqueous species. Above a certain pH, depending on the concentration of carbonate in solution, carbonate does not play a role in the aqueous U(VI) speciation anymore due to the predominance of hydrolysis. TRLFS measurements revealed a clear correlation between sorption behavior and aqueous U(VI) speciation, showing that retention reaches a maximum at pH 10-12, where UO2(OH)3− is the predominant aqueous species. This raised the question whether the strong retention can be achieved by adsorption of an anionic species to the negatively charged mineral surface or rather by precipitation of uranates. By in situ ATR FT-IR and CTR/RAXR experiments the formation of U(VI) precipitates on the mineral surface was observed at U(VI) concentrations of 2×10-5 M and 5×10-5 M, respectively. However, solubility tests at sub-micromolar U(VI) concentrations, which were also applied in the batch sorption experiments, showed that the observed complete U(VI) removal at pH 10-12 cannot be attributed to precipitation of (earth) alkali-uranates from the solution. In order to unambiguously distinguish between surface precipitation and surface complexation, direct spectroscopic investigations of the U(VI) complexes on the Ca-bentonite surface were performed with site-selective TRLFS and EXAFS. The occurrence of luminescence line-narrowing and the frequency of the total symmetric stretch vibration obtained from the site-selective TRLFS emission spectra, indicate the presence of two U(VI) surface complexes. Also EXAFS spectroscopy confirmed the presence of two independent U(VI) sorption species on Ca-bentonite at pH 8-13. With increasing pH, the nature of the retained U(VI) complexes shifts from bidentate inner-sphere surface complexes with an overall equatorial coordination of five adsorbed on aluminol or silanol edge sites to surface complexes with a 4-fold equatorial coordination, resembling the aqueous species UO2(OH)42−. For the first time, a 4-fold coordination in the equatorial plane of U(VI) was univocally proven with the help of a multiple-scattering feature originating from the strong symmetry of the complexes, and without the need for error-prone shell fitting. The lack of scattering paths from the substrate and the comparatively high value for the total symmetric stretch vibration indicate that the high-pH-component is an outer-sphere complex. Concerning the character of the second sorption species at very high pH it was hypothesized that the anionic uranyl hydroxide complexes are mediated to the surface by calcium cations. It was found that calcium sorbs strongly on Ca-bentonite between pH 8 and 13. Also zeta potential measurements showed a partial compensation of the strongly negative surface charge of Ca-bentonite due to adsorption of calcium. U(VI) sorption on kaolinite and muscovite was strongly reduced in the absence of calcium at pH > 10. An increased retention upon addition of calcium proved the sorption enhancing effect of calcium at pH 10-12. Site-selective TRLFS allowed the spectroscopic observation and identification of calcium-induced U(VI) sorption complexes on muscovite. The obtained spectra correspond to the outer-sphere species found on Ca-bentonite. Combining the findings from batch sorption, zeta potential, TRLFS and EXAFS suggests that calcium adsorbs to the mineral surface in the first place, displaying locally positively charged sites which enable an electrostatically driven attachment of anionic uranyl hydroxides. The same effect could also be demonstrated for Np(VI) sorption on muscovite, which was also strongly enhanced in the presence of calcium at pH 9-12. ISA leads to a mobilization of U(VI) at (hyper)alkaline conditions only when present in very high excess of U(VI). A reduction of sorption on Ca-bentonite and the formation of aqueous U(VI)-ISA complexes, detected with TRLFS, occurred at an U:ISA ratio of 1:100,000. Such conditions are not likely to be found in deep geological repository environments. Based on these findings it can be concluded that under certain alkaline repository conditions, where precipitation does not occur (due to very low concentrations or kinetic restraints), U(VI) and Np(VI) are still effectively retained in argillaceous minerals and rocks by adsorption despite the anionic character of prevailing aqueous species. Repulsive forces between the actinide species and the mineral surfaces are overcome by mediating Ca2+. This finding is of great relevance, as also the migration of very small amounts of uranium or neptunium out of waste repositories could lead to a hazardous accumulation in the long term. The achieved knowledge gain concerning radionuclide retention at environmental conditions helps to take the next step towards realistic long-term safety assessment of nuclear waste repositories

Diffusion and Sorption Studies of Cs, Sr and Co in Intact Crystalline Rock

Three cationic tracers, Sr2+, Co2+ and Cs+ were tested with a modified electromigration device by applying 2V, 3V and 4V voltage gradients over an intact Grimsel granodiorite rock sample. An ideal plug-flow model and an advection-dispersion model were applied to analyze the breakthrough curves. Matrix characterization by C-14-PMMA autoradiography and scanning electron microscopy showed that in the centimeter scale of Grimsel granodiorite rock, the interconnected matrix porosity forms a well-connected network for diffusion. Micrometer-scale fissures are transecting biotite and chlorite minerals, indicating sorption of the studied cations. The ideal plug-flow model indicated that the effective diffusion coefficients (De values) for Sr2+, Co2+ and Cs+ tracer ions within the Grimsel granodiorite rock were 3.20 × 10−13 m2/s, 1.23 × 10−13 m2/s and 2.25 × 10−12 m2/s, respectively. De values were also derived from the advection-dispersion model, from which 2.86 × 10−13 m2/s, 1.35 × 10−13 m2/s and 2.26 × 10−12 m2/s were calculated. The diffusion speed for the tracers was in the sequence of Cs+ > Sr2+ > Co2+ that is in the same sequence as their diffusion in diluted water. The distribution coefficients (Kd values) calculated from the models covered the range of two magnitudes (from 10−7 m3/kg to 10−5 m3/kg). The result indicated that the sorption process of the studied elements did not reach equilibrium during the electromigration process, mainly due to the too much acceleration of the migration speed by the voltage gradients applied over the rock sample

Diffusion and Sorption Studies of Cs, Sr and Co in Intact Crystalline Rock

Three cationic tracers, Sr2+, Co2+ and Cs+ were tested with a modified electromigration device by applying 2V, 3V and 4V voltage gradients over an intact Grimsel granodiorite rock sample. An ideal plug-flow model and an advection-dispersion model were applied to analyze the breakthrough curves. Matrix characterization by C-14-PMMA autoradiography and scanning electron microscopy showed that in the centimeter scale of Grimsel granodiorite rock, the interconnected matrix porosity forms a well-connected network for diffusion. Micrometer-scale fissures are transecting biotite and chlorite minerals, indicating sorption of the studied cations. The ideal plug-flow model indicated that the effective diffusion coefficients (De values) for Sr2+, Co2+ and Cs+ tracer ions within the Grimsel granodiorite rock were 3.20 × 10−13 m2/s, 1.23 × 10−13 m2/s and 2.25 × 10−12 m2/s, respectively. De values were also derived from the advection-dispersion model, from which 2.86 × 10−13 m2/s, 1.35 × 10−13 m2/s and 2.26 × 10−12 m2/s were calculated. The diffusion speed for the tracers was in the sequence of Cs+ > Sr2+ > Co2+ that is in the same sequence as their diffusion in diluted water. The distribution coefficients (Kd values) calculated from the models covered the range of two magnitudes (from 10−7 m3/kg to 10−5 m3/kg). The result indicated that the sorption process of the studied elements did not reach equilibrium during the electromigration process, mainly due to the too much acceleration of the migration speed by the voltage gradients applied over the rock sample

Strukturelle Untersuchung der Rückhaltung von Actiniden und ihrer Übergangsmetallhomologe an ausgewählte Alumosilikat-Phasen

Die sichere Endlagerung hochradioaktiver Stoffe ist weltweit eine der großen Herausforderungen des 21. Jahrhunderts. Der abgebrannte Kernbrennstoff ist hoch-radiotoxisch und stellt somit eine Gefährdung für Mensch und Umwelt dar. Daher muss der radioaktive Abfall für bis zu einer Million Jahre von der Umwelt isoliert werden. International wird dafür die Endlagerung in tiefengeologischen Formationen favorisiert. Für ein solches Endlager für radioaktive Abfälle kommen in Deutschland Salz-, Ton- und Kristallinformationen in Frage, welche aufgrund der verschiedenen mineralogischen und geochemischen Bedingungen Radionuklide (RN) unterschiedlich stark immobilisieren. Wesentliche Prozesse sind dabei Ausfällung, Einbau in Festphasen und Sorption an Mineraloberflächen. Für eine belastbare Risikobewertung möglicher Endlagerstandorte sind geeignete Transportmodelle notwendig, welche auf umfangreiche thermodynamische Daten angewiesen sind. Hierfür sind insbesondere Studien zu Wechselwirkungen (WW) von RN mit Mineralphasen im Kristallingestein, d.h. Quarz, Feldspäten, Glimmern, nicht ausreichend verfügbar. Die minoren Actinide Am und Cm liegen in wässriger Lösung grundsätzlich im dreiwertigen Oxidationszustand vor. Außerdem werden unter den zu erwarteten reduzierenden Bedingungen in einem Endlager auch Np zu einem geringen und Pu zu einem nennenswerten Teil dreiwertig vorliegen. Daher beschäftigt sich der erste Teil der Arbeit mit den WW dreiwertiger Actiniden (An(III) = Am, Cm) mit Feldspäten. Der zweite Teil der Arbeit beschäftigt sich mit dem Einfluss von Elektrolyten auf die Rückhaltung von Actiniden an Mineraloberflächen. Dabei wurde zum einen der Einfluss des natürlich häufig auftretenden, anorganischen Liganden Sulfat auf die Sorption von An(III) an das Schichtsilikat (Glimmer) Muskovit untersucht, sowie in einem weiteren Beispiel der Einfluss der Elektrolytzusammensetzung auf die Sorption des Actinids Thorium an Muskovit untersucht. Th liegt in wässriger Lösung ausschließlich vierwertig vor und wird stark hydrolysiert, wodurch die Bildung polynuklearer Spezies begünstigt ist. Methodisch kommen in diesem Teil der Arbeit neben Oberflächenröntgenbeugung (SXRD) auch Alphaspektrometrie und Rasterkraftmikroskopie (AFM) zum Einsatz. Die Ergebnisse der Arbeit leisten einen signifikanten Beitrag zur realistischen Abschätzung der Mobilität drei- und vierwertiger Actiniden im Kristallingestein. Die Ergebnisse der Arbeit werden in Zukunft Simulationen des reaktiven Transports und somit die Auswahl eines geeigneten Standorts für ein Endlager für radioaktiven Abfall unterstützen

Sorption of environmentally relevant radionuclides (U(VI), Np(V)) and lanthanides (Nd(III)) on feldspar and mica

A safe storage of radioactive waste in repositories is an important task to protect humans and the environment from radio- and chemotoxicity. Long-term safety assessments predict the behavior of potential environmental contaminants like the actinides plutonium, uranium, or neptunium, in the near and far field of repositories. For such safety assessments, it is necessary to know the migration behavior of the contaminants in the environment, which is mainly dependent on the aquatic speciation, the solubility product of relevant solid phases, and the retardation due to sorption on surrounding minerals. Thus, an investigation of sorption processes of contaminants onto different minerals as well as the derivation of mineral specific surface complexation model (SCM) parameters is of great importance. Feldspar and mica are widely distributed in nature. They occur as components of granite, which is considered as a potential host rock for a repository in Germany, and in numerous other rocks, and thus also in the far field of nearly all repositories. However, their sorption behavior with actinides has only been scarcely investigated until now. In order to better characterize these systems and subsequently to integrate these minerals into the long-term safety assessments, this work focuses on the investigation of the sorption behavior of U(VI), Np(V), and Nd(III) as analogue for An(III) onto the minerals orthoclase and muscovite, representing feldspars and mica, respectively. All investigations were performed under conditions relevant to the far field of a repository. In addition to the extensive characterization of the minerals, batch sorption experiments, spectroscopic investigations, and surface complexation modeling were performed to elucidate the uptake and speciation of actinides on the mineral surfaces. In addition, the influence of microorganisms naturally occurring on the mineral surfaces and the effect of Ca2+ on U(VI) uptake on the minerals was studied. The obtained sorption curves exhibit a similar characteristic for orthoclase and muscovite. As expected Nd(III) shows the highest amount of sorption followed by U(VI) and finally Np(V). With spectroscopic investigations of the aquatic U(VI) solution in presence of Ca2+, the Ca2UO2(CO3)3 complex could be identified. Furthermore, with spectroscopic methods the U(VI) surface species onto orthoclase could be characterized, of which a novel uranium-carbonate surface species was observed. Based on the results of batch experiments and spectroscopic methods new SCM parameters for the sorption of U(VI), Np(V), and Nd(III) onto orthoclase and for Np(V) and Nd(III) onto muscovite could be derived. SCM parameters for U(VI) sorption onto muscovite confirmed earlier investigations. The obtained SCM parameters increase the amount of data available for sorption processes onto feldspar and mica. With this the relevance of feldspars for the sorption of actinides and lanthanides could be shown. Thus, this work contributes to a better understanding of interactions of actinides and lanthanides, in particular U(VI), Np(V), and Nd(III), with mineral phases ubiquitous in the environment. This in turn adds confidence to long-term safety assessments essential for the protection of humans and the environment from the hazards of radioactive waste

Comparative Analysis of The Self- and Co-assembly of Type-I and Type-III Collagen

Collagen represents the most abundant protein family in the human body which forms 30% of the total protein. Among different types, type-I and type-III are the two most abundant, respectively, in the heterotypic fibril structure. Although many tissues in the human body have a heterotypic form of co-assembled two or more types of collagens, not much is known concerning the heterotypic assembly of two or more types of collagens. Therefore, the purpose of this study is to investigate the characteristics of the co-assembly process of the two main types of collagen. Collagen, which is a major component of an Extracellular Matrix (ECM) protein, also has a self-assembly ability in vitro, and the resulting matrices are used as scaffolds for cell-biological applications, templates for microelectronic applications, coating materials for non-biological surfaces for enhanced bio-compatibility. The assembly process is, so far, mostly monitored turbidimetrically in solution. In this study, by using atomic force microscopy(AFM), custom image analysis, and kinetic modeling, we study the homotypic and the heterotypic assembly of type-I and type-III collagen on muscovite and phlogopite mica surfaces with varying concentrations and ratios of the two collagen types. We found that when assembled individually, type-I collagen nucleates and assembles faster than type-III, and forms thicker fibrils. When the two collagens co-assemble, the fibril thickness and growth rate decrease as the fraction of type-III collagen increases. However, the fibril nucleation rate depends non-monotonically on the type-III fraction, being the highest for an intermediate mixture of types-I and III collagens. These results can be understood based on their amino acid composition, where type-I collagen, being more hydrophobic, nucleates fibrils fast and grows in both longitudinal and lateral directions. In contrast, the more hydrophilic character of type-III collagen limits the lateral growth of fibrils, which in turn makes more monomers available to nucleate additional fibrils. These results demonstrate how subtle differences in physico-chemical properties of similar molecules can be used to fine-tune their assembly behavior