Evaluating the adsorption of Shanghai silty clay to Cd(II), Pb(II), As(V), and Cr(VI): kinetic, equilibrium, and thermodynamic studies.

Abstract

The adsorption properties of Shanghai silty clay (SSC) towards heavy metal ions Cd(II), Pb(II), As(V), and Cr(VI) were investigated by batch experiments. The effects of solid-solution ratio, pH, temperature, reaction time, and metal concentration on sorption were analyzed. In order to better understand the adsorption mechanisms, X-ray diffraction (XRD), scanning electron microscopy (SEM), and X-ray fluorescence (XRF) were used to analyze the soil specimen before and after sorption. Three adsorption kinetic models and three adsorption isotherm models were used to analyze the adsorption characteristics. Thermodynamic parameters including changes in the Gibbs free energy (ΔG0), enthalpy (ΔH0), and entropy (ΔS0) were also calculated. Sorption capacity of SSC was compared with other clay minerals reported in the literatures. The results show that the selectivity sequence is Pb(II) > Cd(II) > As(V) > Cr(VI), with equilibrium sorption capacities of 26.46, 8.90, 2.80, and 1.85mgg-1, respectively. Adsorption is largely effective on the clay surface rather than on the crystals. The clay surface turns to be flat and slippery after adsorption. The Langmuir model shows the best fit for Cd(II) and Pb(II) data, while Freundlich model is more suitable for As(V) and Cr(VI). The optimum solid-solution ratios for sorption of Cd(II), Pb(II), As(V), and Cr(VI) are 15, 6, 40, and 40g L-1, respectively. The optimum pHs for Cd(II), Pb(II), As(V), and Cr(VI) adsorption are 9.0, 6.0, 7.0, and 2.0, respectively. The pseudo-second-order kinetic is found to be the dominant sorption mechanism of these four ions on SSC. For Cd(II) and Pb(II), both particle diffusion and film diffusion are rate-limiting factors, whereas for As(V) and Cr(VI), intraparticle diffusion is the rate-controlling factor. The thermodynamic analysis reveals that the adsorption of Cd(II) and Pb(II) is spontaneous and endothermic and the system disorder increases, while adsorption of As(V) and Cr(VI) is exothermic and the system disorder decreases. Compared with most clay minerals, natural SSC exhibits comparable adsorption capacity and thus can potentially be used as a landfill liner material to retard the migration of heavy metals.