Surface charge and the effect of excess calcium ions on the hydroxyapatite surface

This paper describes the use of surface titration as a more direct probe of the surface chemistry of hydroxyapatite (HA) than zeta-potential measurements. The variation in HA surface charge with pH for two different KCl electrolyte concentrations was determined titrimetrically and the point of zero charge (PZC) found to be at a pH of 7.3±0.1. The curves also demonstrated that HA accumulates positive charge more readily below the PZC than it accumulates negative charge above it. Extended titration data indicated that dissolution occurred more rapidly in increasingly acidic conditions, but was inhibited by increasing electrolyte strength. Similar experiments with 2.5 mM Ca2+ in the electrolyte show that Ca2+ adsorption balances loss of H+ to give a near-neutral surface at any pH above 7 (subject to availability of calcium ions and adsorption sites). The mechanism for adsorption has been shown to be deprotonation of adjacent surface HPO42− sites and subsequent adsorption of a calcium ion to the lattice surface site. Furthermore, inhibition of dissolution under alkaline conditions in the presence of Ca2+ suggested that dissolution was driven by desorption of Ca2+. Modelling of the adsorption/desorption processes demonstrated that in both pure water and under physiological conditions phosphate groups will predominate at the HA surface. Furthermore, the (2 0 0) plane was identified as the likely form of the HA surface. These methodologies and findings are particularly relevant to investigation of biological response with respect to modification of surface hydrophobicity and surface energy or charge.