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Title: Sorption of Ni and Eu to granitic rocks and minerals
Authors: Ebong, Fidelis Sameh
Keywords: CAM modelling
Sorption kinetics
Competitive sorption
Exchange capacity
Issue Date: 2011
Publisher: © Ebong Fidelis Sameh
Abstract: The work presented in this thesis is divided into two parts. The first part is the sorption of Ni and Eu to granitic materials, and cation exchange capacity measurements for powdered and intact samples. The second part is method development on autoradiography. In the first part, static batch sorption experiments were carried out to study the relative sorption properties of different granitic rocks and minerals. Experimental data were described using non-electrostatic correction models such as the Langmuir, Freundlich and Linear models. Sorption data obtained for sorption in a constant pH environment and variable metal concentration were used to test the Component Additive Model (CAM). Sorption test studies carried out using energy dispersive X-ray microanalysis were used to map the sorption of Eu on an intact sample. The results showed the CAM was applicable for Ni sorption to BG but that it was not applicable for Eu sorption to any of the granitic rocks studied. The sorption data fitted the CAM in the following order; BG (1) > GA (0.7) > RG (0.5) > GG (0.2), GrG (0.2) for Ni sorption and RG (0.7) > BG (0.4) > GA (0.2), GG (0.2), GrG (0.2) for Eu sorption to the different granitic rocks. Values in brackets represent the ratio of Rd-predicted/Rd-calculated. Results from the application of the CAM showed it was not possible to predict the Rd of the bulk sample from the component minerals. Desorption studies at constant pH were analysed by calculating the hysteresis H. The results showed that the higher the Rd the higher the hysteresis. Surface complexation using JChess Geochemical Code was used to obtain surface complexation parameters for the metal-solid complex for sorption in variable pH and constant metal concentration. Experimental data were described by the mass action law to obtained proton stoichiometry at which the sorption edge is defined. Results showed the presence of NaCl decreased the sorption of Ni, and increased the sorption of Eu. Sorption kinetics experiments in different carbonate complexing environments were carried out to study the effect of carbonate on Eu sorption capacity and rate of sorption. Data were fitted to first and second order kinetic models to investigate the sorption rates. Results showed the sorption to be fast initially before reaching a steady state after more than 200 hours of equilibration. Kinetic data confirmed the low sorption capacity observed for quartz. Data obtained for sorption in a mixed radionuclide system were modelled using the Linear model and the surface complexation model. The surface complexation constants are correlated to the Rd values obtained from the linear sorption isotherms. Modelling the results using Rdmix and Rdsing showed that sorption was suppressed in a mixed system, with no effect observed for sorption to feldspar in single and mixed systems. Cation exchange capacity (CEC) measurements were undertaken to deduce a correlation between the CEC of powdered rock samples and intact sample using rock beakers developed from the British Geological Survey by applying the Bascomb method in which the pH was buffered to pH 8.1. Normalising the results using the surface area showed that the CEC of the rock beakers was 6 orders of magnitude greater than that of the powdered sample. In the second part, a method for differentiating two or more radionuclides using storage phosphor imaging plates coupled with the Storm Scanner system was tested. Initial results showed that it is possible to differentiate one radionuclide from another in a mixed system using different levels of shielding.
Description: A Doctoral Thesis. Submitted in partial fulfilment of the requirements for the award of Doctor of Philosophy of