Harald Zänker

Sorption behavior of U(VI) on phyllite: experiments and modeling.

The sorption of U(VI) onto low-grade metamorphic rock phyllite was modeled with the diffuse double layer model (DDLM) using the primary mineralogical constituents of phyllite, i.e. quartz, chlorite, muscovite, and albite, as input components, and as additional component, the poorly ordered Fe oxide hydroxide mineral, ferrihydrite. Ferrihydrite forms during the batch sorption experiment as a weathering product of chlorite. In this process, Fe(II), leached from the chlorite, oxidizes to Fe(III), hydrolyses and precipitates as ferrihydrite. The formation of ferrihydrite during the batch sorption experiment was identified by Mössbauer spectroscopy, showing a 2.8% increase of Fe(III) in the phyllite powder. The ferrihydrite was present as Fe nanoparticles or agglomerates with diameters ranging from 6 to 25 nm, with indications for even smaller particles. These Fe colloids were detected in centrifugation experiments of a ground phyllite suspension using various centrifugal forces. The basis for the successful interpretation of the experimental sorption data of uranyl(VI) on phyllite were: (1) the determination of surface complex formation constants of uranyl with quartz, chlorite, muscovite, albite, and ferrihydrite in individual batch sorption experiments, (2) the determination of surface acidity constants of quartz, chlorite, muscovite, and albite obtained from separate acid-base titration, (3) the determination of surface site densities of quartz, chlorite, muscovite, and albite evaluated independently of each other with adsorption isotherms, and (4) the quantification of the secondary phase ferrihydrite, which formed during the batch sorption experiments with phyllite. The surface complex formation constants and the protolysis constants were optimized by using the experimentally obtained data sets and the computer code FITEQL. Surface site densities were evaluated from adsorption isotherms at pH 6.5. The uranyl(VI) sorption onto phyllite was accurately modeled with these newly determined constants and parameters of the main mineralogical constituents of phyllite and the secondary mineralization phase ferrihydrite. The modeling indicated that uranyl sorption to ferrihydrite clearly dominates uranyl sorption, showing the great importance of secondary iron phases for sorption studies.

Study of the solubility of amorphous and crystalline uranium dioxide by combined spectroscopic methods

Colloid formation and solubility of U(IV) in acidic HClO4/NaClO4 solutions are investigated by coulometric titration. Quantification of traces of U(VI) by laser fluorescence spectroscopy proves that the tetravalent state of uranium had been maintained. Laser-induced breakdown detection (LIBD) is applied for the detection of traces of uranium colloids as the pH is increased. The pH values at the onset of colloid formation are used for thermodynamic calculations aimed at determining the solubility products K°sp of crystalline and amorphous uranium dioxides. The particle size of the colloids determined by means of LIBD is taken into account since it influences the solubility product. The results indicate the formation of crystalline UO2(cr) at low pH∼1 (logK°sp= -59.6±1.0) whereas the amorphous hydrous oxide UO2·xH2O(am) is formed at pH ∼ 3 (logK°sp = -54.1 ± 1.0). Measurements by EXAFS, XRD and REM confirm the occurrence of these different phases. The obtained solubility products fit well in the known series of solubility products of the other tetravalent actinides.

The colloid chemistry of acid rock drainage solution from an abandoned Zn–Pb–Ag mine

Abstract Acid rock drainage (ARD) solution from an abandoned ore mine (pH 2.7, SO2−4 concentration 411 mmol/l, Fe concentration 93.5 mmol/l) was investigated by photon correlation spectroscopy, centrifugation, filtration, ultrafiltration, scanning electron microscopy, ICP–MS, AAS, ion chromatography, TOC analysis, and extended X-ray absorption fine structure (EXAFS) spectroscopy. A colloid concentration of ⩾1 g/l was found. The prevailing particle size was

Colloid-borne forms of tetravalent actinides: A brief review

Tetravalent actinides, An(IV), are usually assumed to be little mobile in near-neutral environmental waters because of their low solubility. However, there are certain geochemical scenarios during which mobilization of An(IV) in a colloid-borne (waterborne) form cannot be ruled out. A compilation of colloid-borne forms of tetravalent actinides described so far for laboratory experiments together with several examples of An(IV) colloids observed in field experiments and real-world scenarios are given. They are intended to be a knowledge base and a tool for those who have to interpret actinide behavior under environmental conditions. Synthetic colloids containing structural An(IV) and synthetic colloids carrying adsorbed An(IV) are considered. Their behavior is compared with the behavior of An(IV) colloids observed after the intentional or unintentional release of actinides into the environment. A list of knowledge gaps as to the behavior of An(IV) colloids is provided and items which need further research are highlighted.

Colloid-borne uranium and other heavy metals in the water of a mine drainage gallery

The water of a mine drainage gallery was investigated for its contents of colloid-borne heavy metals with emphasis on uranium. About 1 mg/L of colloid particles of 100 to 300 nm were found. They consist of a matrix of Fe and Al oxyhydroxides and are formed when anoxic slightly acidic shaft waters mix with oxic near-neutral gallery water. The colloid particles bear toxic trace elements such as As, Pb, and Cu. Almost 100% of the As and Pb and about 70% of the Cu contained in the water are colloid-borne. Carbonato complexes prevent the uranyl from being adsorbed on the colloids in the unaltered gallery water. Acidification destroys these complexes: up to 50% of the uranium is attached to the colloids in the slightly acidic pH region. Further acidification converts the uranyl again to a ‘non-colloidal’ form.

Synthesis of Coffinite, USiO4, and Structural Investigations of UxTh(1–x)SiO4 Solid Solutions

The miscibility behavior of the USiO4-ThSiO4 system was investigated. The end members and 10 solid solutions UxTh(1-x)SiO4 with x = 0.12-0.92 were successfully synthesized, without formation of other secondary uranium or thorium phases. Lattice parameters of the solid solutions evidently follow Vegards Law. Investigation of the local structure with EXAFS reveals small differences between the U and Th environment attributed to different atomic radii of the metal atoms but no implications for a miscibility gap. The data provided confirm complete miscibility for the system USiO4-ThSiO4. The structure of the end members was studied in detail with XRD and discussed with special regard to the oxygen positions and the often neglected Si-O bond length. USiO4 could be obtained without UO2 impurities and the lattice parameters derived from Rietveld refinement as c = 6.2606(3) Å and a = 6.9841(3) Å. The Si-O distance in USiO4 appears to be 1.64 Å, which is more reasonable than earlier reported values.

Oxyhydroxy Silicate Colloids: A New Type of Waterborne Actinide(IV) Colloids

Abstract At the near‐neutral and reducing aquatic conditions expected in undisturbed ore deposits or in closed nuclear waste repositories, the actinides Th, U, Np, and Pu are primarily tetravalent. These tetravalent actinides (AnIV) are sparingly soluble in aquatic systems and, hence, are often assumed to be immobile. However, AnIV could become mobile if they occur as colloids. This review focuses on a new type of AnIV colloids, oxyhydroxy silicate colloids. We herein discuss the chemical characteristics of these colloids and the potential implication for their environmental behavior. The binary oxyhydroxy silicate colloids of AnIV could be potentially more mobile as a waterborne species than the well‐known mono‐component oxyhydroxide colloids.

Speciation of Colloid-borne Uranium by EXAFS and ATR-FTIR spectroscopy

De-acidification of acid mine waters transfers dissolved uranium into a colloidal form. Spectroscopic studies on colloid-borne uranium obtained by simulation of mine flooding in the laboratory showed that matrix ions such as sulfate and silicate are not involved in inner-sphere surface sorption complexes of UO22+ on ferrihydrite. At ambient air atmosphere, the data suggest the formation of ternary U(VI) carbonato surface complexes with either monodentate or bidentate coordination of carbonate and uranyl even at moderately acidic conditions. A revised model is proposed for UO22+ sorption on ferrihydrite in the absence of carbonate.