Carbonated calcium apatites doped with a monovalent cation (Li+, Na+, or K+) or a divalent cation (Mg2+ or Zn2+) were prepared in aqueous solution and analysed by powder X-ray diffraction, inductively coupled plasma atomic emission spectroscopy and infrared spectroscopy. The hypothesis that the location of carbonate in the apatite structure, either in place of hydroxide ions in the c-axis channels (A-type substitution) or in place of phosphate (B-type substitution), is affected by the solution energetics of the cation (specifically its enthalpy of hydration) was strengthened by the observation of larger amounts of Atype carbonate in apatites containing the monovalent cations in aqueous solution. It is shown that cations with low negative enthalpies of hydration favour A-type substitution, whereas cations with higher negative hydration enthalpies, such as divalent cations (Mg2+, Zn2+), favour B-type substitution.