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A-type carbonate in strontium phosphate apatites

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Published/Copyright: February 26, 2019
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American Mineralogist
From the journal American Mineralogist Volume 104 Issue 3

Abstract

One of the most important characteristics of the apatite family of minerals is its ability to undergo substitution by ions such as sulfate and carbonate. The substitution of carbonate is particularly important because of the presence of carbonate in bone mineral and the recent suggestion that most of the substituted carbonate resides in the apatite channels (A-type substitution) rather than in place of phosphate (B-type substitution). The possibility of additional channel species or environments in carbonated Ca hydroxylapatite has been pursued via its Sr homolog, which is known to have a larger channel volume and a greater unit-cell a-axial length than its unsubstituted parent. Strontium hydroxyl-, chlor-, and fluorapatites, containing incorporated 13C-carbonate up to 7 wt%, were synthesized by aqueous precipitation reactions in the presence of Na, K, and ammonium counter cations. 13C-labeled carbonate was used to facilitate observation of the solid-state 13C MAS NMR spectra. Band-fitting of the IR carbonate asymmetric stretch ν3 region required the use of eight bands, arranged as four doublets, that are interpreted as representing three channel environments (A-type substitution) and one B-type substitution. The carbonate ν3 region of low Na, carbonated Sr hydroxylapatite contained the high-frequency limbs of the A-type doublets in the area between 1520 cm–1 and the B-type region (1400–1360 cm–1), whereas in the high Na analog the A-type doublets produced a broad high-frequency tail into the B-type region. Similar behavior was exhibited by the chlor- and fluorapatite analogs. Heating samples to 600 °C resulted in the loss of carbonate and conversion to A-type carbonate demonstrating the stability of A-type carbonate at higher temperatures.

Analysis of the populations of A-, A′-, and A″-, and B-sites for the hydroxyl-, chlor-, and fluorapatites, prepared under both low Na and high Na conditions, revealed that high Na/carbonate ratios produce a larger amount of channel substitution, contrary to observations for Ca homologs. It is speculated that multiple A-environments also exist for Ca hydroxylapatite prepared by aqueous precipitation, which is consistent with Fleet’s analysis of apatite prepared at high temperature and high pressure.

Keywords: Strontium; strontium apatite; apatite; IR; NMR; A-type carbonate

Acknowledgments

The authors are indebted to the reviewers, Kyle T. Ashley and an anonymous reviewer, to Stanley and Karen Mertzman and Emily Wilson (Department of Earth and Environment, Franklin and Marshall College) for analytical work, to Kathleen Stepien (Franklin and Marshall College) for technical assistance, to the Camille and Henry Dreyfus Foundation for a Senior Scientist Mentor award (C.H.Y.), and to the Lucille and William Hackman Summer Research Program and the Yoder Student Research Endowment at Franklin & Marshall College for funding.

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Received: 2018-07-06
Accepted: 2018-12-04
Published Online: 2019-02-26
Published in Print: 2019-03-26

© 2019 Walter de Gruyter GmbH, Berlin/Boston

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https://doi.org/10.2138/am-2019-6715
Keywords for this article
Strontium; strontium apatite; apatite; IR; NMR; A-type carbonate

Articles in the same Issue

  1. Letter
  2. Chessboard structures: Atom-scale imaging of homologs from the kobellite series
  3. Special collection: Microporous materials: Crystal-chemistry, properties, and utilizations
  4. Highlighting the capability of zeolites for agro-chemicals contaminants removal from aqueous matrix: Evidence of 2-ethyl-6-methylaniline adsorption on ZSM-12
  5. Special collection: Physics and chemistry of earth's deep mantle and core
  6. Origin and consequences of non-stoichiometry in iron carbide Fe7C3
  7. Special collection: Isotopes, minerals, and petrology: Honoring John Valley
  8. Application of mineral equilibria to estimate fugacities of H2O, H2, and O2 in mantle xenoliths from the southwestern U.S.A.
  9. Review
  10. Composition, paragenesis, and alteration of the chevkinite group of minerals
  11. Articles
  12. Spinel-anorthosites on the Moon: Impact melt origins suggested by enthalpy constraints
  13. Fast diffusion path for water in silica glass
  14. Micro- and nano-scale textural and compositional zonation in plagioclase at the Black Mountain porphyry Cu deposit: Implications for magmatic processes
  15. A XANES and EPMA study of Fe3+ in chlorite: Importance of oxychlorite and implications for cation site distribution and thermobarometry
  16. Sound velocities across calcite phase transitions by Brillouin scattering spectroscopy
  17. Trace element distributions in (Cu)-Pb-Sb sulfosalts from the Gutaishan Au-Sb deposit, South China: Implications for formation of high fineness native gold
  18. A-type carbonate in strontium phosphate apatites
  19. Discovery of a zinc-rich mineral on the surface of lunar orange pyroclastic beads
  20. In-situ mapping of ferric iron variations in lunar glasses using X-ray absorption spectroscopy
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  22. Book Review
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