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Abundant hydration, diffusivity, and volatile phase composition render the surface of calcium phosphates (CPs) a complex dynamic region. Three CP powders were analyzed using X-ray photoelectron spectroscopy (XPS) and ion scattering spectroscopy (ISS) with regard to their surface compositions and fine structures hydroxyapatite (HAp), amorphous CP (ACP), and a CP formed under the same conditions as ACP but allowed to ripen into HAp (ACP → HAp). XPS analyses revealed that the Ca/P atomic ratio in the 2-10 nm-thick layers of the