Lignite utilisation for binding of radionuclides and uranium determination by adsorptive stripping chronopotentiometry

This work in its first part deals with non-energetic use of young brown coal - lignite. The goal of the work was to perform a complex physical and chemical characterisation of the Slovak lignite (deposit Cary) which could contribute to rts use in binding of radionuclides in the environment. The characteristics of Slovak lignite were compared to leonardite (Gascoyne, USA) and Czech lignite (the area of Mikulcice). In the samples the residual humidity was determined. as well. as the content of ashes. representation of selected inorganic (As, Ba, Cd, Co, Cr, Cu, Ni, Pb and Zn) as well as organo-elements (C, H, N, 0, S) and crystalline forms of inorganic phase in lignite. The specific surface (BET isotherm) of lignite was determined, representation of total and free humic acids and their cation exchange capacity. The samples underwent al.so gamma-spectrometric analysis (40K, 226Ra, 228Ac, 137Cs and 60Co). Using the radio-indicator method (85Sr and 137Cs) the kinetics of sorption of Cs+ and Sr+ ions in Slovak lignite was studied. The efficiency of sorption for both cations on lignite was evaluated on the basis of constructed sorption isotherms. The sorption of Cs+ ions on Slovak lignite is more suitable for the Freundlich type of isotherm, in case of Sr+ ions the sorption is better described by Langmuir isotherm. The results of sorption experiments on lignite in comparison with clinoptilolite and montmorillonite K-10 showed a more efficient sorption for Sr Ions. despite the more coarse-grained fraction of this matrix. This finding supports the possibility of lignite application for binding of a quite mobile radiostrontium, which may be applied for construction of radioactive waste repositories or for remediation of contaminated soils. The second part of the work deals with the development and validation of new fast and reliable electrochemical method of uranium determination in natural waters. It is based on physical adsorption of created complex of uranium -cupferron on amalgam work electrode with the value of accumulation potential +200 mV (vs. Ag/AgCl). The work includes optimisation of the accumulation and regeneration time, the regeneration potential, the pH value of supporting electrolyte and concentration of used complexing agent (cupferron). The interference impacts of selected cations on uranium determination by means of adsorptive stripping chronopotentiometry (AdSC) have been also studied. The method is linear within the range of up to 50 μg dm-3, relative standard deviation for 10 μg dm-3 of uranium is 5.2 % (n=10, accumulation time 60 s). Experimentally, the value of limit of detection was determined for uranium (1.2 μg dm-3) as well as the value of limit of quantification (3.6 μg dm-3). Using AdSC, the content of uranium was successfully determined in the sample of natural mineral water with high content of salts. The newly designed electrochemical method of determining uranium was validated by means of ICP- MS analysis and spectrophotometric determination of uranium with arsenazo III. The AdSC method may be used for uranium monitoring in waters and after potential further optimisation of sample pre-treatment also in sediments and in soil. (author)