Mechanisms of soil humic acid adsorption onto montmorillonite and kaolinite

To explore the adsorption mechanisms of a soil humic acid (HA) on purified kaolinite and montmorillonite, a combination of adsorption measurements, attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy and isothermal titration calorimetry (ITC) was employed at pH 4.0, 6.0 and 8.0. The adsorption affinities and plateaus of HA on the two clays increased with decreasing pH, indicating the importance of electrostatic interaction. The effects were more significant for kaolinite than for montmorillonite. The substantial adsorption at pH 8.0 indicated hydrophobic interaction and/or H-bonding also played a role. The ATR-FTIR results at pH 8.0 showed that the Si-O groups located at basal faces of the two clays were involved in the adsorption process. For kaolinite, at pH 4.0 and 6.0, HA adsorption occurred via OH groups on the edge faces and basal octahedral faces (both positively charged), plus some adsorption at Si-O group. The exothermic molar adsorption enthalpy decreased relatively dramatically with adsorption up to adsorption values of 0.7 μmol/g on montmorillonite and 1.0 μmol/g on kaolinite, but the decrease was attenuated at higher adsorption. The high exothermic molar enthalpy of HA binding to the clays was ascribed to ligand exchange and electrostatic binding, which are enthalpy-driven. At high adsorption values, JGHA adsorption by hydrophobic attraction and H-bonding also occurs.