Abstract
SUMMARY: The variation in the solubility of aluminium in some acid soils of south‐eastern Australia has been investigated. The hypothesis was that leaching of silicic acid influenced the extent of clay decomposition, and hence aluminium solubility, in accord with Le Chatelier's principle. In lower rainfall areas (< 800 mm) control of Al solubility was consistent with a poorly crystalline kaolinite as the source phase, while at higher rainfall (> 1200 mm) it was consistent with gibbsite control. However, soluble silica concentrations were too high for gibbsite and kaolinite to be thermodynamically stable phases. The hypothesis was modified to take account of a quasi‐equilibrium in the open soil system, in which clay dissolution and A1 solubility appear to depend on the relative rates of H+ input and of silica leaching. These may result in a supersaturated, or possibly even undersaturated system, at any point in time. The relative sizes of the organic sink and mineral Al source determine the influence of organic matter on Al solubility.