This report reviews general approaches for determining the chemical species of ionic materials and outlines a feasible approach to the analytical speciation of Cr(III) and (VI), and Fe(II) and (III) in an aqueous solution. The results of the speciation are related to existing models through redox electrode potential measurements. An ion chromatographic technique based on the separation of anionic species was selected for the speciation. Nonspecific and specific detection alternatives are discussed, and detection limits are projected into the low parts per billion range.