Modelling the solid–solution distributions of protons, aluminium, base cations and humic substances in acid soils

wham , an equilibrium chemical model for soils, waters and sediments, centred on a discrete-site/ electrostatic model of humic substances (HS), has been used to analysae batch titration data for organic and mineral horizons of acid soils. In most cases, tolerable fits were obtained by optimizing the soil contents of HS and aluminium, while keeping the model parameters (site densities, equilibrium constants, electrostatic terms) fixed. The optimized contents agreed reasonably with those estimated by chemical extraction. For some mineral soil samples, low in HS and high in aluminium, fitting of the titration data was improved by assuming the formation and dissolution of A1(OH)₃ and adjusting its solubility product. Solid-solution distributions of base cations (Na⁺, Mg²⁺, K⁺, Ca²⁺, NH⁺⁴) could be explained by non-specific counterion accumulation, with a small degree of selectivity. The WHAM sub-model for fulvic acid sorption accounted approximately for observed aqueous-phase concentrations of organic carbon and organically-complexed aluminium.