The Effect of Supersaturation on Apatite Crystal Formation in Aqueous Solutions at Physiologic pH and Temperature

The importance of supersaturation in the dynamics of apatite precipitation from aqueous solutions is well-established. To determine whether this parameter has a comparable impact on the concomitant development of the textural properties of this phase, such as crystal size and shape, we investigated mineral accretion in synthetic solutions seeded with 0.67 g/L apatite over a range of supersaturations at pH 7.4 and 37°C. A dual specific-ion electrode-controlled titration method was used to maintain the seeded reactions under the following solution conditions: 1.0 to 1.8 mmol/L Ca²⁺, 0.67 to 1.2 mmol/L total phosphate (PO₄), Ca/PO₄ (initial) = 1.5, 143 mmol/L KNO₃, and 10 mmol/L HEPES. Samples were collected for chemical and textural analyses when the seed apatite was reduced by new accretions to 1/2,1/4,1/8,1/16, and 1/32 of the total solids in suspension. All new accretions were found to be apatitic. At the lowest supersaturation, accretion occurred primarily by growth of the seed crystals. However, at the highest supersaturation examined, the crystals at the end of the experiments were actually smaller, on average, than the original seeds, even though the total mass increased 32-fold. The results suggest that proliferation of new crystals supplanted growth of the seed crystals as supersaturation was increased. The results also suggest that differences in tissue fluid supersaturation may contribute to the large disparity in dimensions between dentin and enamel apatite crystals.