Some ionic effects on small water cluster systems formed around sodium(I), calcium(II), and iron(II) cations have been investigated using the density functional theory. By assuming that the numbers of water molecules in the first and the second water layers are 6 and 12, respectively, it is shown that (i) the Ca(II) aqueous cluster shrinks and its volume becomes similar to that of a pure (H2O)18 cluster whereas the Fe(II) and Na(I) aqueous clusters expand; (ii) owing to the water dipole--dipole interactions induced by the ion in the second water layer binding, the ionization strength of the Ca(II) aqueous cluster is close to that of Fe(II) but sufficiently higher than that of Na(I); (iii) the isotropicity of s-type Ca(II) and Na(I) cation orbitals as the cause of the reduction in water rotational rigidity in the ion--water bonding has been clarified by analyzing the charge transfer and non interacting kinetic energy. By considering the three ionic effects, we predict that the Ca(II) ion is one of the more competitive water cationic impurities in the PEMFC membrane.