Kinetics and equilibrium modeling of uranium(VI) sorption by bituminous shale from aqueous solution

Sorption of U(VI) onto a bituminous shale (BS) from a nuclear power plant project site in Black Sea region was investigated for potential risk assessment when it releases into the environment with contaminated ground and surface water. The sorption characteristics of the BS for U(VI) recovery were evaluated as a function of contact time, adsorbent dosage, initial concentration, pH and temperature. Kinetic results fit better with pseudo-second-order model rather than pseudo-first-order. The possibility of diffusion process was analyzed based on Weber-Morris intra-particle diffusion model. The McKay equation assuming film- and intraparticle diffusion better predicted the data than the Vermeulen approximation presuming surface diffusion. Equilibrium sorption data were modeled according to the Langmuir, Dubinin-Radushkevich (D-R) and Freundlich isotherm equations. Sorption capacity increased from 0.10 to 0.15 mmol g−1 in 298-318 K temperature range. FT-IR analysis and pH dependent sorption studies conducted in hydroxide and carbonate media revealed that U(VI) species were sorbed in uranyl and its hydroxo forms on the BS. Desorption studies showed that U(VI) leaching with Black Sea water was negligible from the loaded BS. The activation parameters (Ea, ΔH∗ and ΔG∗) estimated from diffusion coefficients indicated the presence of an energy barrier in the sorption system. However, thermodynamic functions derived from sorption equilibrium constants showed that overall sorption process was spontaneous in nature and entropy controlled.