Calcium modulates interactions between bacteria and hydroxyapatite.

Bacterial adhesion onto hydroxyapatite is known to depend on the surface properties of both the biomaterial and the bacterial strain, but less is known about the influence of the composition of the aqueous medium. Here, the adhesion of Streptococcus mutans and 3 different Lactobacilli on powdered hydroxyapatite was shown to change with Ca2+ concentration. The effect depends on the surface properties of each strain. Adhesion of Lactobacillus fermentum and salivarius (and of Streptococcus mutans at low Ca2+) was enhanced with increasing Ca2+ concentration. Lactobacillus casei was efficiently removed by adhesion on hydroxyapatite, even without Ca2+ addition, and the effect of this ion was only marginal. The results are interpreted in terms of Ca2+-mediated adhesion, and relative to the hydrophobic properties of each strain and the electrical properties of the bacterial and solid surfaces (electrophoretic mobility).

Surface properties of various powdered hydroxyapatites.

Electrophoretic mobilities of various synthetic and semisynthetic hydroxyapatites (Ca10(PO4)6(OH)2, HAP) suspended in aqueous solutions have been measured as a function of pH and calcium concentration. The studied powders differ in particle size, crystallinity degree and surface contamination (carbonate). When equilibrated in mineral acids or bases, a large plateau of negative mobility is observed in the pH range 5-8, with increasing negative values at higher pH. Only in the case of the sample composed of nanoparticles, positive mobility obtains at pH < 8.9. When Ca2+ is added, positive mobility values are observed for all samples, and a bell-shaped profile results as a function of pH. Two possible models are explored to describe the results: the Nernstian approach, which assumes solubility equilibrium and surface potentials determined by the three potential-determining ions (Ca2+, PO3-4, and OH-), and the surface complexation approach, based on the idea of negligible phase transfer of structural phosphate. The Nernstian model is inadequate, whereas a very simple surface complexation model based on the equations Ca5(PO4)+3 = Ca4(PO4)-3 + Ca2+,Ca4(PO4)-3 + H+ = Ca4(PO4)2(PO4H),Ca5(PO4)+3 + OH- = Ca5(PO4)3(OH),coupled with a very simple electrical double layer, model suffices to reproduce the bell-shaped profile of the mobility as a function of pH in the presence of added calcium salts. The results also show that the sample composed of nanoparticles exchanges ions more easily with the solution, without reaching the solubility equilibrium in the explored timespans. In the presence of soluble phosphate salts, it is postulated that the same surface ensembles define the surface charge, with participation of phosphate as described by the equation Ca5(PO4)+3 + PO3-4 = Ca4(PO4)-3.HAP is just one member of a family of calcium phosphates with different (Ca)/(P) ratios. Electrophoretic mobilities of another member, tricalcium diphosphate, Ca3(PO4)2, were also measured and shown to be described by the same basic model. Comparison with previous literature data shows that the negative plateau in the mobility is a general feature of many HAP samples at low Ca2+, again in agreement with the surface complexation model. FTIR data demonstrates that surface phosphate indeed undergoes protonation, as postulated in the model.

Natural materials for treatment of industrial effluents: comparative study of the retention of Cd, Zn and Co by calcite and hydroxyapatite. Part I: batch experiments.

This work explores the heavy metal retention capacity of materials developed from minerals that are abundant in nature, with low cost and minimum environmental impact. To accomplish this objective we have: (a) characterized commercial samples of calcite (CA) and hydroxyapatite (HAP)--including their surface properties (BET area, electrophoretic mobility, SEM, and X-ray energy dispersive spectroscopy); and, (b) qualified and quantified the interaction of Cd, Zn and Co with calcite (CaCO3) and hydroxyapatite [Ca5(PO4)3OH] through batch experiments, in a range of metal concentrations (4Zn>Co and Cd>Zn approximately Co, respectively. Retention increased with pCa and pH and could be modeled by: (a) a non-ideal ion exchange mechanism (Me/Ca) for the adsorption of Cd, Zn and Co onto CA; and, (b) a mechanism of non-ideal ion exchange and specific adsorption (Me/Ca and identical with PO4O-Me) in the case of HAP. The pH dependence is indirect in CA and is related to its solubility changes (pCa increases with pH, and so does sorption of Cd, Zn and Co). Both materials, HAP and CA, can be used for heavy metal retention. The former has better performance for water treatment due to its greater efficiency for the retention of Cd, Zn and Co (over two orders of magnitude per gram of material) and its lower solubility in a wide range of pH (6

Removal of oxovanadium(IV) from aqueous solutions by using commercial crystalline calcium hydroxyapatite.

The interaction of oxovanadium(IV) (VO(2+)) in aqueous solution with commercial calcium hydroxyapatite (CAP) has been studied. VO(2+) ions are adsorbed on the surface of CAP by coordination to OH groups, without modification of the crystalline lattice. The extent of the adsorption is followed by chemical analysis, ESR and IR spectroscopy. Results are compared with those obtained for VO(2+)/synthetic calcium hydroxyapatite (HAP), reported by us in previous works. The uptake is better than the observed for HAP. The maximum adsorption is observed at pH 3.5 and 288 K. We conclude that VO(2+) is indeed adsorbed on CAP and the extent of adsorption depends on the pH and temperature.