Adsorption of copper, zinc, and cadmium on goethite, aluminum-substituted goethite, and a system of kaolinite-goethite: Surface complexation modeling

Goethite, aluminum-(Al)-substituted goethite (GA2), and a system of kaolinite-goethite were examined for their ability to adsorb copper (Cu), zinc (Zn), and cadmium (Cd) as a function of pH, in two ionic strengths and two different metal concentrations. Specific surface area was deter-mined by BET-N-2, whereas the charge development on the solid surface was studied in the pH range similar to 3.5 to similar to 10.0 by potentiometric titration under continuous flow of argon. Constant capacitance (CCM) and the double-layer model (DLM) were used to fit the titration and adsorption data with the help of the least-square optimization program 2 FITEQL32. In both models, surface site density was fixed at Ns = 2.31 sites nm(-2), whereas for CCM capacitance density was set at C = 1.06. Alternatively, bibliographic suggestions for these two parameters were examined. Aluminum-substituted goethite exhibited higher specific surface area and adsorbed all three metals in lower pH values than the other solids. Moreover, GA2 exhibited point of zero salt effect (PZSE) higher than goethite, approaching that corresponding to Al2O3, possibly due to Al-substitution, and the system exhibited PZSE values much higher than kaolinite, approaching that corresponding to goethite. The adsorption order for all three solids was Cu > Zn > Cd in any case, thus more Cu is adsorbed at a certain pH than Zn and even more than Cd, whereas the increase of metal concentration shifts the adsorption curve toward higher pH values. Constant capacitance described the titration data satisfactorily, but by altering the Ns and C values, the fit became worse. Adsorption data are described by CCM, by emphasizing the formation of monodentate surface complex. Bidentate complex, in most of the cases, was of no importance in describing the data despite the evidence of its presence in recent spectroscopic studies for Cu and Cd on goethite. Alteration of Ns and C values worsened the fit in any case, and bidentate complex vanished. The DLM exhibited the worse fit in any case.