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Growth dynamics of vaterite in relation to the physico-chemical properties of its precursor, amorphous calcium carbonate, in the Ca-CO3-PO4 system

  • Yuki Sugiura EMAIL logo , Kazuo Onuma and Atsushi Yamazaki
Published/Copyright: February 18, 2016
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American Mineralogist
From the journal American Mineralogist Volume 101 Issue 2

Abstract

Vaterite is one of three non-hydrate calcium carbonate crystalline polymorphs and is formed as an initial phase under pseudo-biological conditions. However, biological hard tissues that use vaterite are rare; the reason for vaterite rarely appearing in vivo is still unclear. There is consensus that, in phosphate-containing solutions, vaterite barely forms and amorphous calcium carbonate (ACC), the precursor of crystalline calcium carbonate and considered as aggregation of growth unit of vaterite, is stabilized. In this study, to clarify the biomineralization process, we investigated how phosphate acts as an inhibitor of vaterite growth. We measured vaterite growth rates in situ and estimated the essential crystal growth parameter, edge free energy, in the Ca-CO3-PO4 system in relation to the physico-chemical properties of ACC. The effects of PO4 on the ACC structure and dynamics were also observed.

Co-existed PO4 reduced the growth rate of vaterite even when it was added in µM-scale concentrations. The surface free energy of vaterite increased with increasing PO4 concentration and was 10× higher in a 10 μM PO4-containing solution than in a PO4-free solution. Spectroscopic analyses showed that the chemical bonds in ACC particles were drastically changed by the addition of μM-scale PO4, and the particles could no longer transform into vaterite. We conclude that PO4 inhibits vaterite growth and changed the ACC structure. And the original growth units of vaterite were also modified to the other structures. Thus, vaterite crystals could not grow by association of these growth units, which resulted in an increase in the apparent surface free energy of vaterite.

Keywords: Vaterite; crystal growth; intermediate phase; biomineralization

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

Acknowledgments

We thank A. Ito and Y. Sogo for their assistance with the optical microscopy experiments. A. Oyane helped with FE-SEM/EDX measurements. We also thank T. Goto for SAXS analysis, N. Sugimura and T. Shibue for Raman and NMR measurements. We thank K. Nakamura and Y. Kimura for their advice. This research was partially funded by the Material Characterization Central Laboratory, Waseda University and a grant-in-aid for doctoral students (DC2) and start-up for young researchers (No. 15H06488) from the Japan Society for the Promotion of Science (JSPS), Ministry of Education, Culture, Sports, Science and Technology (MEXT), Grant No. 25–2283.

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  1. Manuscript handled by Mickey Gunter

Received: 2014-8-1
Accepted: 2015-9-1
Published Online: 2016-2-18
Published in Print: 2016-2-1

© 2016 by Walter de Gruyter Berlin/Boston

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https://doi.org/10.2138/am-2016-5184
Keywords for this article
Vaterite; crystal growth; intermediate phase; biomineralization

Articles in the same Issue

  1. Highlights and Breakthroughs
  2. The deep continental crust has a larger Mg isotopic variation than previously thought
  3. Article
  4. Magnesium isotopic composition of the deep continental crust
  5. Review
  6. Cancrinite-group minerals: Crystal-chemical description and properties under non-ambient conditions—A review
  7. Amorphous Materials: Properties, Structure, and Durability
  8. Nepheline structural and chemical dependence on melt composition
  9. Chemistry and Mineralogy of Earth's Mantle
  10. Some thermodynamic properties of larnite (β-Ca2SiO4) constrained by high T/P experiment and/or theoretical simulation
  11. Minerals in the Human Body
  12. Growth dynamics of vaterite in relation to the physico-chemical properties of its precursor, amorphous calcium carbonate, in the Ca-CO3-PO4 system
  13. Special Collection: Perspectives on Origins and Evolution of Crustal Magmas
  14. Mafic replenishments into floored silicic magma chambers
  15. Special Collection: Perspectives on Origins and Evolution of Crustal Magmas
  16. Hafnium, oxygen, neodymium, strontium, and lead isotopic constraints on magmatic evolution of the supereruptive southern Black Mountains volcanic center, Arizona, U.S.A.: A combined LASS zircon–whole-rock study
  17. Special Collection: Perspectives on Origins and Evolution of Crustal Magmas
  18. Deciphering magmatic processes in calc-alkaline plutons using trace element zoning in hornblende
  19. Special Collection: Geology and Geobiology of Lassen Volcanic National Park
  20. The Lassen hydrothermal system
  21. Article
  22. Maruyamaite, K(MgAl2)(Al5Mg)Si6O18(BO3)3(OH)3O, a potassium-dominant tourmaline from the ultrahigh-pressure Kokchetav massif, northern Kazakhstan: Description and crystal structure
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