Methods are developed for determining quantitative relative concentrations of elements in the aluminosilicate matrix and in nonmatrix or surface material of coal fly ash. The dependence of total element concentration on particle size and the solubility of elements in solutions of HC1 and HF are discussed. The results indicate greater than 70% of the Ti, Na, K, Mg, Hf, Th, and Fe is associated with the aluminosilicate matrix. More than 70% of the Ca, Sc, Sr, La, the rare earth elements, and probably Ni appears to be associated with an acid-soluble phase, which has the same particle size distribution as the aluminosilicate phases. More than 70% of the As, Se, Mo, Zn, Cd, W, V, U, and Sb are associated with surface material on the ash particles. The elements Mn,