Carbonate in Synthetic and Biological Apatites

The crystal chemistry of carbonate in Ca apatites, including Na-free and Na-bearing hydroxylapatite (CHAP) and Na-bearing fluorapatite (CFAP) and chlorapatite (CCLAP), has been investigated by Fourier transform infrared (FTIR) spectroscopy and single-crystal X-ray structure, using crystals synthesised from carbonate-rich melts at 1 GPa, 1400 1000°C. The carbonate ion substitutes for both the X (OH, F, Cl) anion species in the apatite channel (type A carbonate) and the phosphate group (type B carbonate). The type A carbonate ion is oriented in the channel with two oxygen atoms close to the c-axis, and the type B carbonate ion is located close to the sloping faces of the substituted phosphate tetrahedron, with details varying with composition series. Sodium promotes the uptake of type B carbonate and also has a profound effect on FTIR spectra. Crystal compositions correspond approximately to the substitution formula Ca10-(y+z)Nay z[(PO4)6-(y+2z)(CO3)y+2z][X2-2x(CO3)x], with x ≈ y up to 1.0 and z ≈ 0.0 for CHAP, x ≈ y ≈ 4z ≈ 0.4 for CCLAP, and x ≈ y ≈ 2z ≈ 0.1 for CFAP, for equivalent conditions of synthesis. The sodium cation and A and B carbonate ion defects are locally coupled in all three composition series to facilitate charge compensation and minimise the effects of spatial accommodation. Synthetic Na-bearing type A-B CHAP with x ≈ y ≈ 0.5 has a similar chemical composition and FTIR spectrum to biological apatite.