Eight dissolution models of calcium apatites (both fluorapatite and hydroxyapatite) in acids were drawn from the published literature, analyzed and discussed. Major limitations and drawbacks of the models were conversed in details. The models were shown to deal with different aspects of apatite dissolution phenomenon and none of them was able to describe the dissolution process in general. Therefore, an attempt to combine the findings obtained by different researchers was performed which resulted in creation of the general description of apatite dissolution in acids. For this purpose, eight dissolution models were assumed to complement each other and provide the correct description of the specific aspects of apatite dissolution. The general description considers all possible dissolution stages involved and points out to some missing and unclear phenomena to be experimentally studied and verified in future. This creates a new methodological approach to investigate reaction mechanisms based on sets of affine data, obtained by various research groups under dissimilar experimental conditions.

In this study, morphological and chemical changes in teeth enamel exposed to alkaline agents, with or without surfactants, have been investigated. In addition, chemical effects of the organic surface layer, i.e. plaque and pellicle, were also investigated.

The present study was conducted using several techniques: Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD) and scanning electron microscopy (SEM).

From XPS-measurements, it was found that exposure to alkaline solutions resulted in a massive removal of carbon from the tooth surface, and that the addition of surfactants increased the rate under present conditions. Based on the results from the FTIR-analysis, no substitution reactions between phosphate, carbonate and hydroxide ions in the enamel apatite could be detected. From a minor SEM-analysis, degradation and loss of substance of the enamel surface was found for the exposed samples. From XRD-analysis, no changes in crystallinity of the enamel apatite could be found between the samples.

The findings in this study show that exposure to alkaline solutions results in a degradation of enamel surfaces very dissimilar from acidic erosion. No significant erosion or chemical substitution of the apatite crystals themselves could be discerned. However, significant loss of organic carbon at the enamel surface was found in all exposed samples. The degradation of the protective organic layer at the enamel surface may profoundly increase the risk for caries and dental erosion from acidic foods and beverages.

The effect of calcite supernatant, calcium, and carbonate ions on the hydroxyapatite (HA) zeta potential without and in the presence of sodium oleate (1x10(-4) mol L(-1)) was examined within the pH range from 4 to 12. The interpretation of results was based on the HA surface and oleate solution chemistry, and on some floatability tests. HA, with different positive and negative surface sites formed depending on its solubility and pH, had a negative zeta potential over the whole pH range. This mineral is not naturally floatable (flotation recovery, 5%<R<18%). The oleate ions (Ol(-)), present in a very low concentration in an acidic medium (pH from 4.8 to 6), chemisorb individually on HA surface centers [triple bond]Ca(+), [triple bond]HPO(4)Ca(+), and [triple bond]OH(2)(+), increasing the negative zeta potential of the mineral. Within the pH range from 7 to 9, the dominant oleate species Ol(-) ion and ion-molecule complex, H(Ol)(2)(-), adsorbed on HA by head groups toward the solid and associated due to chain-chain interaction in hemimicelles, made the HA surface with zeta potential about -22/-23 mV, and more floatable (R=80-100%) than in 4<pH<7 (R=15-35%) or in pH>9.3. The HA surface is less negatively charged in calcite supernatant than in water from pH 6.6 to 9.2 due to the adsorption on HA negative surface active centers ([triple bond]HPO(4)(-) and [triple bond]PO(4)(2-)) of the Ca(2+), and CaOH(+) ions (present in the calcite supernatant), producing more surface sites [triple bond]HPO(4)Ca(+), [triple bond]PO(4)Ca, [triple bond]HPO(4)CaOH, and [triple bond]PO(4)(-) CaOH, and new centers [triple bond]HPO(4)CaHCO(3) and [triple bond]PO(4)(-) CaHCO(3). In the presence of 1x10(-3) mol L(-1) CaCl(2), the HA sample has positive zeta potential, the same as calcite from the same deposit, up to IEP at pH 11.25. Carbonate ions (1x10(-3) mol L(-1) Na(2)CO(3)) do not affect the HA zeta potential. However, a possible process can be the ion-exchange reaction between bicarbonate (or carbonate) and some anion from the surface sites formed on HA. The obtained values of the HA zeta potential with the collector (1x10(-4) mol L(-1) Na-oleate) added into hydroxyapatite/calcite supernatant suspensions corroborate the weak chemisorption of Ol(-) and H(Ol)(2)(-). The likely processes in this system also are the ion-exchange reactions on [triple bond]HPO(4)CaOH and [triple bond]PO(4)(-) CaOH, [triple bond]HPO(4)CaHCO(3) and [triple bond]PO(4)(-) CaHCO(3) between oleate ion and surface hydroxyl and bicarbonate ions, surface and bulk precipitations of calcium oleate, Ca(Ol)(2), and the surface and bulk precipitations of Ca[H(Ol)(2)(-)](2) over the pH range from 7 to 9. Calcite supernatant does not influence natural floatability of the mineral. However, calcite supernatant depresses the hydroxyapatite flotation in the presence of 1x10(-4) mol L(-1) Na-oleate (pH 9, R approximately 50%), a likely result of the weak chemisorption due to the steric effect of heterogeneous HA surface formed in calcite supernatant, Ca(Ol)(2) and Ca[H(Ol)(2)(-)](2) surface and bulk precipitations.

A synthetic fluorapatite was prepared that undergoes a phase transformation generated during a dialysis step. A surface layer with the composition Ca9(HPO4)2(PO4)4F2 is formed, which is suggested to form as one calcium atom is replaced by two protons. A surface complexation model, based upon XPS measurements, potentiometric titration data, batch experiments, and zeta-potential measurements was presented. The CaOH and OPO3H2 sites were assumed to have similar protolytic properties as in a corresponding nonstoichiometric HAP (Ca8.4(HPO4)1.6(PO4)4.4(OH)0.4) system. Besides a determination of the solubility product of Ca9(HPO4)2(PO4)4F2, two additional surface complexation reactions were introduced; one that accounts for a F/OH ion exchange reaction, resulting in the release of quite high fluoride concentrations (approximately 1 mM) that turned out to be dependent on the surface area of the particles. Furthermore, to explain the lowering of pHiep from around 8 in nonstoichiometric HAP suspensions to about 5.7 in FAP suspensions, a reaction that lowers the surface charge due to the readsorption of fluoride ions to the positively charged Ca sites was introduced: triple bond CaOH2++F-<-->triple bond CaF+H2O. The resulting model also agrees with predictions based upon XPS and ATR-FTIR observations claiming the formation of CaF2(s) in the most acidic pH range.

The acid-base properties of synthetically prepared and well-characterized hydroxyapatite (HAP) in contact with KNO3 solutions were investigated at 25 degrees C, through potentiometric titrations, zeta-potential measurements, and surface complex modeling. Aliquots of suspension were withdrawn every 0.5 pH unit during the titration procedure and analyzed for calcium and phosphate. It was found that, even for rapid titration experiments, a remarkable amount of H+ ions (H+dissol.) is consumed in the bulk solution in reacting with species coming from the dissolution of HAP. These H+ ions must be taken into account in the H+ mass balance, in order for true value for the point of zero charge (pzc=6.5+/-0.2) and consequently true value for the surface charge (sigma0) to be obtained. Besides the conventional potentiometric titration technique, it was found that pzc may be determined much more easily as the intersection point of the suspension titration curve and the blank one modified to include the amount of H+dissol. obtained at one ionic strength. Finally, a surface complexation model was proposed for the development of surface charge. Experimental data were satisfactorily fitted by using the value of 4.2 F m-2 for the capacitance.