Ammonium-calcium exchange equilibria in soils and weathered pumices that differ in cationexchange materials

The retention of NH₄+ and Ca²+ on soil and weathered pumice samples containing constant and/or variable charge components was measured in different NH₄CI-CaCl₂ solutions. The NH₄+/Ca²+ selectivity of each sample was evaluated using a quotient of the partition of NH₄+ on the exchange sites and in the solution relative to that of Ca²+. It increased with decreasing pH and increasing NH₄Cl-CaCl₂ concentration for a given equivalent fraction of NH₄+ in the solution. These effects were quantitatively explained in terms of the changes of NH₄+ and Ca²+ concentrations in the solution and in the diffuse double-layer of the ion-exchange material as predicted by the law of mass action and the electric double layer theory. The NH₄+/Ca²+ selectivity of different exchange materials showed a similar variation among their exchange sites and increased in the order humus, allophane and imogolite (Si/Al ratio 0.5) < allophane (Si/Al ratio 1.0), montmorillonite < vermiculite, illite < halloysite. The origin of negative charge, the steric features around the exchange sites and clay-humus interaction are suggested as being important in determining the NH₄+/Ca²+ selectivity.