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Solid-state NMR and IR spectroscopic investigation of the role of structural water and F in carbonate-rich fluorapatite

Harris E. Mason^1,2,*, Francis M. McCubbin¹, Alexander Smirnov^3, and Brian L. Phillips^1,2

¹ Department of Geosciences, State University of New York, Stony Brook, New York 11794-2100, U.S.A.
² Center for Environmental Molecular Science, State University of New York, Stony Brook, New York 11794-2100, U.S.A.
³ Geophysical Laboratory, Carnegie Institution for Science, 5251 Broad Branch Road N.W., Washington, D.C. 20015, U.S.A.

Correspondence: ^* E-mail: hmason{at}ic.sunysb.edu

We have studied the substitutions in a natural well-crystallized carbonate-containing apatite-(CaF) (var. staffelite) using infrared (IR) and solid-state nuclear magnetic resonance (NMR) spectroscopic techniques. Our results show the presence of both A- and B-type carbonate plus a large amount of structural water (0.44 pfu). This sample also contains 0.21 pfu excess F, but only weak C-F dipolar coupling is observed indicating that a tetrahedral CO₃F^3– complex does not occur. ¹⁹F NMR results indicate the presence of a second F environment in the apatite structure at a concentration similar to that of B-type carbonate but which does not differ from channel F in terms of coupling to ³¹P or ¹H.

Key Words: Apatite-(CaF) • IR spectroscopy • NMR spectroscopy