Characterisation of Kaolinite and Adsorption of Europium on Kaolinite

Markus Olin, Eini Puhakka, Jarmo Lehikoinen, Esa Puukko, Martti Hakanen, Antero Lindberg

Research output: Book/ReportReport


Kaolinite is a common fracture mineral in many crystalline rocks and, thus, a potential sorbent for groundwater solutes. The low cation-exchange capacity makes kaolinite a good mineral to study sorption by inner-sphere complexation of multivalent ions, such as trivalent actinides or their analogues, the trivalent lanthanides. The sorption of europium and americium on kaolinite has been studied previously by Puukko and Hakanen (2001a) using a natural kaolinite, KGa-1b (from the Clay Minerals Society, USA). This work describes the determination of surface-charging mechanism and surface acidity constants for KGa-1b kaolinite, and adsorption of Eu(III) on both the natural (KGa-1b) and its acid-conditioned form (HKGa). The ionic strength of the background NaNO3 electrolyte used in these titrations was 0.05 M, 0.1 M and 0.5 M. The surface acidity of kaolinite was explained using the FITEQL software by applying the 1-pK model. The optimized concentration of surface sites was close to a value previously reported for KGa-1b kaolinite. The adsorption modelling of europium was carried out by adopting one surfacecomplexation and one cation-exchange reaction. In the acidic pH range, sorption of europium decreased with increasing ionic strength of the NaNO3 solution, which is an indication of the dominance of cation exchange or outer-sphere complexation. At the lowest ionic strength, the sorption was reversible. In the 0.1 M and 0.5 M NaNO3 solutions, the sorption of europium in the basic pH range was only partly reversible, or desorption kinetically slow. The degree of irreversibility increased with increasing pH and ionic strength. A diffuse-layer model was readily fitted on the per-cents sorbed scale (default in FITEQL), but the results were not as good on a Kd scale, especially at circumneutral pH values. In the water analysis of the batch titration of KGa-1b kaolinite, the main observed elements were aluminium and zinc. The concentrations of Al and Zn decreased with pH. Lanthanides were detectable in the solution only in the acidic pH range 3-6 and showed a decreasing concentration with increasing pH, in good agreement with sorption behaviour of added europium. KGa-1b contained organic and iron impurities, which did not have an effect on the sorption of europium. The results from molecular-level modelling were used for further development of surface-complexation models for both kaolinite surface charging and adsorption of europium. The experimental part of this study was carried out at the University of Helsinki (Laboratory of Radiochemistry) and at Geological Survey of Finland, and the modelling part at VTT.
Original languageEnglish
Place of PublicationOlkiluoto
Number of pages62
Publication statusPublished - 2007
MoE publication typeD4 Published development or research report or study

Publication series

SeriesPosiva Working Report


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