-Parallel experiments on human tooth enamel with sp.g. > 2.95 and synthetic hydroxyapatite have been carried out to study the substitution of CO~-for OH-, produced at 1000°C in dry C02, with the complementary use of neutron diffraction, x-ray diffraction, infrared spectroscopy and thermochemical techniques.It was verified that the substitution (i) is CO B-++ 2(OH-) and is completely reversible on specimen exposure to H20 vapor at 1000°C, (ii) takes place with the carbon atom on or near the hexad axis, (ii) places one CO~-group per unit cell in an ordered fashion and so changes the space group from P63/m to one without a screw axis, (iii) was consistent, by its incompleteness, with the occurrence of substitution of 02-for 2(OH-) in 25 to 40% of the unit cells, (iv) produced similar marked changes in the neutron powder diffraction patterns of both tooth enamel and hydroxyapatite, and (v) took place at a site where only a minor portion of the CO B -in normal, untreated human tooth enamel occurs.From comparative Rietveld analysis results from x-ray and neutron powder diffraction patterns it is suggested that the carbon atom of this A-site CO B -is near 0,0,0.12 and the CO B -plane makes an angle of zi8 ° with the o direction.On being heated at 400°C in H20 vapor, tooth enamel retained much of its CO B-but its a lattice parameter changed from 9.445(3) ~ to 9.420(i~ ~, essentially that of hydroxyapatite.After once being heated at high temperatures, "tooth enamel" and hydroxyapatite showed similar responses to various treatments, including carbonation. After heating, more 8-Ca3(PO4) 2 was found in the tooth enamel specimen.Comparative weight change, IR, and other data for tooth enamel and hydroxyapatite heated in He, then in CO2, and then in H20 vapor showed a 20% or more deficiency of structural OH-in the untreated tooth enamel.