Gibbs free binding energy and adsorption energy between cations and charged soil particles were used to evaluate the interactions between ions and soil particles. The distribution of Gibbs free adsorption energies could not be determined experimentally before the development of Wien effect measurements in dilute soil suspensions. In the current study, energy relationships between heavy metal ions and particles of Hapli-Udic Argosol （Alfisol） and Ferri-Udic Argosol were inferred from Wien effect measurements in dilute suspensions of homoionic soil particles （〈 2 μm） of the two soils, which were saturated with ions of five heavy metals, in deionized water. The mean Gibbs free binding energies of the heavy metal ions with Hapli-Udic Argosol and Ferri-Udic Argosol particles diminished in the order of Pb^2＋ 〉 Cd^2＋ 〉 Cu^2＋ 〉 Zn^2＋ 〉 Cr^3＋, where the range of binding energies for Hapli-Udic Argosol （7.25-9.32 kJ mol^-1） was similar to that for Ferri-Udic Argosol （7.43-9.35 kJ mol^-1）. The electrical field-dependent mean Gibbs free adsorption energies of these heavy metal ions for Hapli-Udic Argosol and for Ferri-Udic Argosol descended in the order： Cu^2＋ 〉 Cd2^＋ 〉 Pb^2＋ 〉 Zn^2＋ 〉 Cr^3＋, and Cd^2＋ 〉 Cu^2＋ 〉 Pb^2＋ 〉 Zn^2＋ 〉 Cr^3＋, respectively. The mean Gibbs free adsorption energies of Cu^2＋, Zn^2＋, Cd^2＋, Pb^2＋, and Cr^3＋ at a field strength of 200 kV cm^-1, for example, were in the range of 0.8-3.2 kJ mo1^-1 for the two soils.
WANG Yu-JunLI Cheng-BaoWANG WeiZHOU Dong-MeiXU Ren-Kou
The study was to investigate the adsorption behavior of arsenite （As（HI）） and arsenate （As（V）） on two variable charge soils, i.e., Haplic Acrisol and Rhodic Ferralsol at different ionic strengths and pH with batch methods. Results indicated that the amount of As（HI） adsorbed by these two soils increased with increasing solution pH, whereas it decreased with increasing ionic strength under the acidic condition. This suggested that As（Ⅲ） was mainly adsorbed on soil positive charge sites through electrostatic attraction under the acidic condition. Moreover, intersects of As（Ⅴ） adsorption-pH curves at different ionic strengths （a characteristic pH） are obtained for both soils. It was noted that above this pH, the adsorption of As（Ⅴ） was increased with increasing ionic strength, whereas below it the reverse trend was true. Precisely the intersect pH was 3.6 for Haplic Acrisol and 4.5 for Rhodic Ferralsol, which was near the values of PZSE （soil point of zero salt effect） of these soils. The effects of ionic strength and pH on arsenate adsorption by these soils were interpreted by the adsorption model. The results of zeta potential suggested that the potential in adsorption plane becomes less negative with increasing ionic strength above soil PZSE and decreases with increasing ionic strength below soil PZSE. These results further supported the hypothesis of the adsorption model that the potential in the adsorption plane changes with ionic strength with an opposite trend to surface charge of the soils. Therefore, the change of the potential in the adsorption plane was mainly responsible for the change of arsenate adsorption induced by ionic strength on variable charge soils.
