Adsorption / Modelling / Uranium(VI) / Natural substrates / Surface complexation / Partition coefficientsSummary. Component additivity (CA) and generalised composite (GC) approaches to deriving a suitable surface complexation model for description of U(VI) adsorption to natural mineral assemblages are pursued in this paper with good success. A single, ferrihydrite-like component is found to reasonably describe uranyl uptake to a number of kaolinitic iron-rich natural substrates at pH > 4 in the CA approach with previously published information on nature of surface complexes, acid-base properties of surface sites and electrostatic effects used in the model. The GC approach, in which little pre-knowledge about generic surface sites is assumed, gives even better fits and would appear to be a method of particular strength for application in areas such as performance assessment provided the model is developed in a careful, stepwise manner with simplicity and goodness of fit as the major criteria for acceptance.

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The uptake of U(VI) as UO! + on a natural complex mineral assemblage has been studied using batch selective chemical extraction techniques and secondary ion mass spectroscopy (SIMS). Sediments used in the study consisted of a quartz/mica schist collected from the locale of the Koongarra Uranium ore body, Alligator Rivers Uranium Province, Northern Territory, Australia. The bulk sediment was gravity separated into four size fractions, with attention focused on the nominally <25 μπι and 250-1000 μηι fractions of the bulk sample, in order to assess the effects of particle size on uranium uptake. Investigation of the kinetics of elemental release in the presence of selective extractants show that uranium is bound largely within the iron and aluminium oxyhydroxides of the assemblage, with a highly mobile fraction of this associated with aluminol sites. SIMS analysis of the natural substrate confirms that significant quantities of aluminium are present in surface layers. The effect of particle size on the uptake of uranium indicates very little change with respect to particle size. This finding may be attributed to the presence of highly porous surface coatings.

Analytical electron microscopy (AEM) has been employed to characterize the distribution of U(VI) on several mineral substrates, including standard kaolinite samples and weathered rock samples from Koongarra, Australia. Results of this study reveal that pre-existing impurity phases play a significant role in the uptake of U(VI) on standard kaolinite samples. Using a natural sample from the weathered zone of the Koongarra uranium deposit, we have also demonstrated that U(VI) sorption is controlled by iron oxyhydroxides (predominantly goethite) which constitute a small fraction of the sample. Limited sorption of U(VI) was observed on the clay minerals of this substrate. Uptake of U(VI) by goethite increases with total uranium content up to the point of uranium precipitation, after which it decreases dramatically. Uranium precipitation is indicated by the appearance of a uranyl oxyhydroxide phase.