Approaches to the construction of thermodynamic models for sorption of trace-element cations on carbonates are considered. To calculate thermodynamic equilibria by the method of Gibbs free-energy minimization, the existing database of reaction constants and thermodynamic potentials was extended. Different types of models are illustrated by the example of precipitation of Cd, Cu, Pb, and Zn from the water of a drainage stream flowing out of the impoundment of barite-polymetallic ore-dressing wastes. It is shown that the mobility of metals in such cases can be controlled by their sorption by calcite present in bottom sediments and suspension. Any approach can be successfully applied to both the modeling of experimental data on cation sorption and the prediction of the ecologo-geochemical situation in the districts of dressing works.