Jump to ContentJump to Main Navigation
Show Summary Details
More options …

American Mineralogist

Journal of Earth and Planetary Materials

Ed. by Baker, Don / Xu, Hongwu / Swainson, Ian


IMPACT FACTOR 2018: 2.631

CiteScore 2018: 2.55

SCImago Journal Rank (SJR) 2018: 1.355
Source Normalized Impact per Paper (SNIP) 2018: 1.103

Online
ISSN
1945-3027
See all formats and pricing
More options …
Volume 102, Issue 10

Issues

Substitution of sulfate in apatite

Linh K. Tran / Kathleen R. Stepien / Melissa M. Bollmeyer / Claude H. Yoder
Published Online: 2017-10-02 | DOI: https://doi.org/10.2138/am-2017-6088

Abstract

The substitution of sulfate in apatite is of potential importance in synthetic biomaterials used in bone repair and reconstruction. The counter ion (e.g., Na+, K+, Mg2+, Sr2+) in the sulfate reagent may also be used as a source of medically beneficial ions. An understanding of the structural parameters controlling sulfate substitution is also important in expanding our knowledge beyond the substitution of carbonate in apatites.

The incorporation of sulfate in calcium and strontium hydroxylapatites, prepared in aqueous solution at pH 9, was verified by combustion analysis of sulfate, infrared and Raman spectroscopy, and by determination of unit-cell parameters. Sulfate could not be incorporated into barium hydroxylapatite because of the preferential formation of BaSO4.

The amount of sulfate substituted in the apatite was affected by the mole ratio of sulfate to phosphate in the reaction mixture and by the nature of the counter ion in the sulfate reagent. When sodium is the counter ion in the sulfate reagent, the molar amounts of both sodium and sulfate in the product apatite can be explained by assuming charge compensation by sodium ions and sulfate displacement of phosphate and calcium. With lithium as the counter ion, a greater molar amount of lithium than sulfate is incorporated into the apatite, an observation that requires an additional charge-compensation mechanism. With potassium and rubidium as counter ions, less of the counter ion is incorporated than sulfate, probably a result of less favorable accommodation of the larger cation in the apatite structure.

The maximum molar amount of sulfate incorporated in hydroxylapatite (prepared in the presence of Na+) is more than three times lower than the maximum molar amount of carbonate that can be incorporated, a difference that can be explained by the relative solubilities of the substituted apatites. The unit-cell parameters determined for both sulfated calcium and strontium hydroxylapatites synthesized with the sodium counter ion show a slight increase in the a-axis length and a nearly constant c-axis length with increasing sulfate content. The difference in the variation of unit-cell parameters with anion content can be rationalized by the difference in size of the anion.

The results indicate that sulfate can be incorporated into biomaterials such as apatite or in composites with calcium sulfate and that the design of new apatites and composites could include the use of medically desirable counter cations.

Keywords: Apatite; sulfate; incorporation of sulfate; unit cell; IR; strontium apatite; sulfated apatite; calcium sulfate-apatite composite; Biomaterials—mineralogy meets medicine

Special collection papers can be found online at http://www.minsocam.org/MSA/AmMin/special-collections.html.

References cited

  • Alshemary, A.Z., Goh, Y-F., Akram, M., Razali, I.R., Kadir, M.R.A., and Hussain, R. (2013) Microwave assisted synthesis of nano-sized sulphate doped hydroxyapatite. Materials Research Bulletin, 48, 2106–2110.Google Scholar

  • Arnett, T.R. (2008) Extracellular pH regulates bone cell function. The Journal of Nutrition, 138, 4155–4185.Google Scholar

  • Dasent, W.E. (1982) Inorganic Energetics, 2nd ed. Cambridge University Press, New York.Google Scholar

  • De Maeyer, E.A.P., Berbeeck, R.M.H., and Pieters, I.Y. (1996) Carbonate and alkalimetal incorporation in calciumhydroxyapatite. Trends in Inorganic Chemistry, 4, 157–171.Google Scholar

  • Fillingham, Y.A., Lenart, B.A., and Gitelis, S. (2012) Function after injection of benign bone lesions with a bioceramic. Clinical Orthopaedics and Related Research, 470, 2014–2020.Google Scholar

  • Fleet, M.E., and Liu, X. (2007) Coupled substitution of type A and B carbonate in sodium-bearing apatite. Biomaterials, 28, 916–926.Google Scholar

  • Flora, N.J., Yoder, C.H., and Jenkins, H.D.B. (2004) Lattice energies of apatites and the estimation of ΔHf0(PO43,g). Inorganic Chemistry, 43, 2340–2345.Google Scholar

  • Goldenberg, J.E., Wilt, Z., Schermerhorn, D.V., Pasteris, J.D., and Yoder, C.H. (2015) Structural effects on incorporated water in carbonated apatites. American Mineralogist, 100, 274–280.Google Scholar

  • Holland, T.J.B., and Redfern, S.A.T. (1997) Unit cell refinement from powder diffraction data: the use of regression diagnostics. Mineralogical Magazine, 61, 65–77.Google Scholar

  • Khorari, S., Cahay, R., Rulmont, A., and Tarte, P. (1994) The coupled isomorphic substitution 2(PO4)3− → (SO4)2− + (SiO4)4− in synthetic apatite Ca10(PO4)6F2: a study by X-ray diffraction and vibrational spectroscopy. European Journal of Solid State Inorganic Chemistry, 31, 921–934.Google Scholar

  • Klement, R. (1939) Natrium-Calcium-sulfatapatit Na6Ca4(SO4)6F2. Naturwissenschaften, 27, 568.Google Scholar

  • Kreidler, E.R., and Hummel, F.A. (1970) The crystal chemistry of apatite: structure fields of fluor- and chlorapatite. American Mineralogist, 55, 170–184.Google Scholar

  • Kuo, T.F., Lee, S.Y., Wu, H.D., Porna, M., Wu, Y.W., and Yang, J.C. (2015) An in vivo swine study for xeno-grafts of calcium sulfate-based bone grafts with human dental pulp stem cells (hDPSCs). Materials Science and Engineering C. Materials of Biological Applications, 10, 19–23.Google Scholar

  • LeGeros, R.Z., Trautz, O.R., LeGeros, J.P., Klein, E., and Shirra, W.P. (1967) Apatite crystallites: effects of carbonate on morphology. Science, 155, 1409–1411.Google Scholar

  • LeGeros, R.Q., Ito, A., Ishikawa, K., Sakae, R., and LeGeros, J.P. (2009) Fundamentals of hydroxyapate and related calcium phosphates. In B. Basu, D. Katii, and A. Kumar, Eds., Advanced Biomaterials: Fundamentals, Processing, and Applications, p. 19–52, Wiley, New York.Google Scholar

  • Liu, Y., Wang, A., and Freeman, J.J. (2009) Raman, MIR, and NIR spectroscopic study of calcium sulfates: gypsum, bassanite, and anhydrite, 40th Lunar and Planetary Science Conference, 2128.Google Scholar

  • Marcus, Y., Jenkins, H.D.B., and Glasser, L. (2002) Ion volumes: a comparison. Journal of the Chemical Society, Dalton Transaction, 3795–3798.Google Scholar

  • Mayer, I., Berger, U., Markitziu, A., and Gedalia, I. (1986) The uptake of lithium ions by synthetic carbonated hydroxyapatite. Calcified Tissue International, 38, 293–295.Google Scholar

  • McConnell, D. (1937) The substitution of SiO44andSO42 groups for PO43 groups in the apatite structure; ellestadite, the end-member. American Mineralogist, 22, 977–986.Google Scholar

  • Montel, G., Bonel, G., Heughebaert, J.C., Trombe, J.C., and Rey, C. (1981) New concepts in the comoposition, crystallization and growth of the mineral component of calcified tissues. Journal of Crystal Growth, 53, 74–99.Google Scholar

  • Pan, Y., and Fleet, M.E. (2002) Compositions of the apatite-group minerals: substitution mechanisms and controlling factors. Reviews in Mineralogy and Geochemistry, 48, 13–49.Google Scholar

  • Parsons, J.R., Ricci, J.L., Alexander, H.J., and Bajpai, P.K. (1988) Osteoconductive composite grouts for orthopedic use. Annals of the New York Academy of Sciences, 100B, 1911–1921.Google Scholar

  • Pasteris, J.D. (2016) A mineralogical view of apatitic biomaterials. American Mineralogist, 101, 2594–2610.Google Scholar

  • Pasteris, J.D., Yoder, C.H., and Wopenka, B. (2014) Molecular water in nominally unhydrated carbonated hydroxylapatite: The key to a better understanding of bone mineral. American Mineralogist, 99, 16–27.Google Scholar

  • Ricci, J.L., Alexander, H., Nadkarni, P., Hawkins, M., Turner, J., Rosenblum, S., Brezenoff, L., DeLeonardis, D., and Pecora, G. (2000) Biological mechanisms of calcium-sulfate replacement by bone. In J.E. Davies, Ed., Bone Engineering, Toronto, EM2 Inc., p. 332–344.Google Scholar

  • Roobottom, H.K., Jenkins, H.D.B., Passmore, J., and Glasser, L. (1999) Thermochemical radii of complex ions. Journal of Chemical Education, 76, 1570–1573.Google Scholar

  • Shepherd, J.H., Shepherd, D.V., and Best, S.M. (2012) Substituted hydroxyapatites for bone repair. Journal of Materials Science Materials in Medicine, 23, 2335–2347.Google Scholar

  • Simpson, D.R. (1968) Substitutions in apatite: I. Potassium-bearing apatite. American Mineralogist, 53, 432–444.Google Scholar

  • Thomas, M.V., and Puleo, D.A. (2009) Calcium sulfate: Properties and clinical applications. Journal of Biomedical Materials research Part B, 88B, 597–610.Google Scholar

  • Toyama, T., Kameda, S., and Nichimiya, N. (2013) Synthesis of sulfate-ionsubstituted hydroxyapatite from amorphous calcium phosphate. Bioceramics Development and Applications, S1:011, .CrossrefGoogle Scholar

  • Urban, R.M., Turner, T.M., Hall, D.J., Inoue, N., and Gitelis, S. (2007) Increased bone formation using a calcium sulfate and calcium phosphate composite graft. Clinical Orthopaedics and Related Research, 459, 110–117.Google Scholar

  • Verbeeck, R.M.H., De Maeyer, E.A.P., and Driessens, F.C.M. (1995) Stoichiometry of potassium- and carbonate-containing apatites synthesized by solid state reactions. Inorganic Chemistry, 34, 2084–2088.Google Scholar

  • Whyte, J., Hadden, D.J., Gibson, I.R., and Skakle, J.M.S. (2008) Synthesis and stability of potassium/carbonate co-substituted hydroxyapatites. Key Engineering Materials, 361-363, 207–210.Google Scholar

  • Yang, H.L., Zhu, X.S., Chen, L., Chen, C.M., Mangham, D.C., Coulton, L.A., and Aiken, S.S. (2012) Bone healing response to a synthetic calcium sulfate/tricalcium phosphate graft material in a sheep vertebral body defect model. Biomedical Material Research B. Applied Biomaterials, 100B, 1911–1921.Google Scholar

  • Yoder, C.H., and Rowand, J.P. (2006) Application of the simple salt lattice energy approximation to the solubility of minerals. American Mineralogist, 91, 747–752.Google Scholar

  • Yoder, C.H., Landes, N.R., Tran, L.K., Smith, A.K., and Pasteris, J.D. (2016) The relative stabilities of A- and B-type carbonate substitution in apatites synthesized in aqueous solution, Mineralogical Magazine, 80, 977–983, .CrossrefGoogle Scholar

  • Zyman, Z.Z., and Tkachenko, M.V. (2013) Sodium-carbonate co-substituted hydroxyapatite ceramics. Processing and Application of Ceramics, 7, 153–157.Google Scholar

About the article

Received: 2017-01-24

Accepted: 2017-06-06

Published Online: 2017-10-02

Published in Print: 2017-10-26


Citation Information: American Mineralogist, Volume 102, Issue 10, Pages 1971–1976, ISSN (Online) 1945-3027, ISSN (Print) 0003-004X, DOI: https://doi.org/10.2138/am-2017-6088.

Export Citation

© 2017 by Walter de Gruyter Berlin/Boston.

Comments (0)

Please log in or register to comment.
Log in