Surface charge characteristics of kaolinitic tropical soils

Surface charge properties of four representative kaolinitic soils from the humid tropics (Brazil) were investigated by a methodology involving independent measurements of net total permanent and variable charge components. Permanent structural charge was determined by Cs⁺ adsorption, whereas variable charge was quantified by simultaneous proton titration and background electrolyte (LiCl) adsorption measurements. Data were obtained for homoionic soils suspended in LiCl solutions of ionic strength 1-10 mmol L^-1 and pH value 2-6. Corrections were made in the titration data for proton consumption resulting from dissolution and aqueous-phase complexation reactions. Conjunctive use of proton titration and electrolyte adsorption data yielded independent assessments of proton surface charge densities and points of zero charge. The surface charge data were tested successfully for consistency with the law of surface charge balance. Three of the soils exhibited similar surface charge behavior, with no pronounced effect of differences in either organic C or Fe and aluminum oxide content. One soil containing significant manganese oxides showed points of zero charge well below those of the other three soils. The point of zero net charge (p.z.n.c) for the soils was ≤4, lower than values reported for specimen kaolinite. The point of zero net proton charge (p.z.n.p.c.) increased with decreasing ionic strength. In all cases, the presence of small quantities of structural charge in 2:1 clay minerals had a significant effect on surface charge properties; e.g., for all soils, p.z.n.c. < p.z.n.p.c. These characteristics of surface charge were shown to be consistent with the behavior of a mixture of kaolinite, organic matter, and a small quantity of 2:1 clay minerals. In conformity with the law of surface charge balance, ionic strength effects were found to be removed by plotting net adsorbed ion charge against net proton surface charge density.