Abstract The aims of the present investigation were to assess the applicability of the metastable equilibrium solubility (MES) concept for the carbonated apatites (CAPs) over a range of pH and a wide range of solution fluoride concentrations and to examine the hypothesis that, in the presence of solution fluoride, a surface complex with the stoichiometry of fluorapatite (FAP) governs the MES behavior. Two CAP samples were prepared by precipitation from reaction media containing calcium nitrate (Ca(NO3)2·4H2O) and sodium phosphate (NaH2PO4·H2O) at two different levels of sodium bicarbonate. The MES distributions of the two CAP preparations were determined by equilibrating approximately 10 mg of CAP powder in 2 L of 0.1 M acetate buffers (ionic strength=0.50 M) at pH 4.5 and 5.5 and at various levels of calcium, phosphate, and fluoride. The fluoride concentrations ranged from 0.03 to 12 ppm. From the compositions of the equilibrating buffer solutions, ion activity products based upon the stoichiometries of hydroxyapatite (HAP) and FAP were calculated in an attempt to determine the correct function governing the dissolution of the CAP preparations. The results of this study demonstrated that both CAP preparations exhibit the MES distribution phenomenon in solution media of varying pH and fluoride concentrations. Furthermore, the experimental MES data obtained with both CAP preparations at the lower pH (4.5) and at higher solution fluoride levels (≥0.1 ppm) were essentially superimposable when plotted against the ion activity product based upon the stoichiometry of FAP, suggesting that in the presence of solution fluoride the MES governing surface complex may be an entity possessing a stoichiometry approximated by that of FAP. When the HAP stoichiometry was assumed to represent the surface complex, good superposition of the data was not possible.