A reinvestigation of the type specimen of wadalite, ideally Ca12Al10Si4O32Cl6, from Tadano, Fukushima Prefecture, Japan, reveals that it has well-defined chemical sector zoning. The mineral occurs in skarn xenoliths in two-pyroxene andesite and forms tris-tetrahedral crystals up to 1 mm in size. The mineral is cubic, I¯43d, with a = 12.009(2) Å, V = 1731.8(8) Å3 and Z = 2. The zoning is divided into two sectors, {21¯1} and {211}, on the basis of back-scattered-electron images. The {21¯1} sector is more enriched in Fe3+, Si, Mg and Cl, and depleted in Al than the {211} sector. The empirical formulae yielded by the averaged compositions for the {21¯1} and {211} sectors are: Ca12.01(Al7.88$\hbox{Fe}_{{\rm 0}{\rm. 99}}^{{\rm 3 +}} $Si4.51Mg0.56Ti0.05)Σ13.99O32.22Cl5.55 and Ca12.05(Al8.42$\hbox{Fe}_{{\rm 0}{\rm. 85}}^{{\rm 3 +}} $Si4.20Mg0.44Ti0.04)Σ13.95O32.19Cl5.38, respectively. Compositional variations in the wadalite grains suggest that the Si contents are controlled mainly by the substitution T(Al,Fe3+) + W□ ↔ TSi + W(Cl,F). The presence of sector zoning suggests that the wadalite grew during rapid non-equilibrium crystallization.

A CO-bearing member of the hydroxylapatite–hydroxylellestadite series occurs as a Si-rich part of a hydroxylapatite–hydroxylellestadite series mineral (hydroxylapatitess) in a skarn xenolith from Tadano, Fukushima Prefecture, Japan. Hydroxylapatitess is composed of Si-poor and Si-rich parts. The Si-poor part is F-rich hydroxylapatite. The infrared spectrum of the Si-rich part demonstrates the presence of B-type CO3. A representative analysis of the Si-rich part yielded the empirical formula Ca4.989[(PO4)1.315 (SiO4)0.848 (SO4)0.368(CO2.943)0.480]∑3.011(OH0.629 Cl0.264 F0.107)∑1.000 on the basis of 8 cations, assuming Si = S + C. There is a very strong inverse correlation between Si and P in both the Si-poor and Si-rich parts. These data indicate that the substitution mechanism (SO4,CO3)2– + (SiO4)4– = 2(PO4)3– probably occurs in hydroxylapatite ss. Therefore, it was concluded that the Si-rich part corresponds to a CO3-bearing hydroxylapatite–hydroxylellestadite series mineral with CO3 partially replacing SO4. Most of the Si-rich part shows CO3 > SO4 and its composition approaches Ca5(SiO4)1.5(CO3,SO4)1.5(OH,Cl,F).