This study aimed to: determine the Mg and CO3 distribution in the outer (surface), middle, and inner (closest to the enamel-dentin junction, EDJ) layers of human enamel; and determine the factors affecting the incorporation of Mg into synthetic apatites and the consequence of such incorporation on the properties of the apatites. Results demonstrated that the concentrations of Mg, CO3, and organic components increased from the surface to the inner layers close to the EDJ and a difference in crystallinity from the outer to the inner layers. Initial results indicated that the extent of dissolution of the inner layer enamel is greater than that in the outer or surface enamel. Results on synthetic apatites showed the following: (1) Limited Mg incorporation into apatite was dependent on solution [Mg/Ca] molar ratio, temperature, pH, and the presence of CO3 or fluoride (F); (2) incorporation of Mg causes reduction in crystallinity and an increase in the extent of dissolution of the apatite; (3) the negative effect of Mg on the properties of apatites is synergistic to that of CO3 and antagonistic to that of F; and (4) exposure to acid of Mg-containing apatites causes the dissolution of Mg-rich apatite and precipitation of Mg-poor apatite. The observed decrease in the [Mg/Ca] of enamel and synthetic apatites after acid exposure may explain the observed 'preferential loss' of Mg and CO3 in the initial stages of caries.