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PO4 adsorption on the calcite surface modulates calcite formation and crystal size

  • Yuki Sugiura EMAIL logo , Kunio Ishikawa , Kazuo Onuma and Yoji Makita
Published/Copyright: September 27, 2019
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American Mineralogist
From the journal American Mineralogist Volume 104 Issue 10

Abstract

Calcium carbonate (CaCO3) and particularly its stable phase, calcite, is of great geological significance in the deep carbon cycle since CaCO3 from biomineralized shells and corals form sedimentary rocks. Calcite also attracts attention in medical science and pharmacy as a primary or intermediate component in biomaterials because it possesses excellent biocompatibility along with suitable physicochemical properties. Calcite blocks have already been used during surgical procedures as a bone substitute for reconstructing bone defects formed by diseases and injury. When producing CaCO3 biomaterials and bioceramics, in particular, in vivo control of the size and polymorphic nature of CaCO3 is required. In this study, we investigated the effects of PO4 on calcite formation during the phase conversion of calcium sulfate anhydrate (CaSO4, CSA), which is sometimes used as a starting material for bone substitutes because of its suitable setting ability. CSA powder was immersed in 2 mol/L Na2CO3 solution containing a range of PO4 concentrations (0–60 mmol/L) at 40 °C for 3 days. The treated samples were investigated by X‑ray diffraction, Fourier-transform infrared spectroscopy, X‑ray fluorescence spectroscopy, and thermal analysis. In addition, the fine structures of the treated samples were observed by field-emission scanning electron microscopy, and the specific surface area was measured. We found that PO4, which is universally present in vivo, can modulate the calcite crystal size during calcite formation. A fluorescence study and calcite crystal growth experiments indicated that PO4 adsorbs tightly onto the surface of calcite, inhibiting crystal growth. In the presence of high PO4 concentrations, vaterite is formed along with calcite, and the appearance and stability of the CaCO3 polymorphs can be controlled by adjusting the PO4 concentration. These findings have implications for medical science and pharmacology, along with mineralogy and geochemistry.

Keywords: Calcite; morphology, phosphate; phase transformation; fabrication; calcium carbonate; Biomaterials—Mineralogy Meets Medicine

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

Acknowledgments and Funding

We thank Y. Uryu and T. Nakanishi for helping with FTIR measurement. This study is financially supported by priority issues of Health Research Institute, National Institute of Advanced Industrial Science and Technology (AIST) and, KAKENHI for Young Researcher (B), JP16K20505 and for Young Researcher, JP19H19081, respectively. This study is partially supported by the Research Center for Industrial Science & Technology, Kagawa Industry Support Foundation (RIST Kagawa).

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Received: 2019-02-20
Accepted: 2019-06-17
Published Online: 2019-09-27
Published in Print: 2019-10-25

© 2019 Walter de Gruyter GmbH, Berlin/Boston

Articles in the same Issue

  1. Carbonation and the Urey reaction
  2. Carbonation and decarbonation reactions: Implications for planetary habitability
  3. PO4 adsorption on the calcite surface modulates calcite formation and crystal size
  4. High-pressure Raman and Nd3+ luminescence spectroscopy of bastnäsite-(REE)CO3F
  5. Precipitates of α-cristobalite and silicate glass in UHP clinopyroxene from a Bohemian Massif eclogite
  6. Solubility behavior of δ-AlOOH and ɛ-FeOOH at high pressures
  7. Analyst and etching protocol effects on the reproducibility of apatite confined fission-track length measurement, and ambient-temperature annealing at decadal timescales
  8. Identification of interstratified mica and pyrophyllite monolayers within chlorite using advanced scanning/transmission electron microscopy
  9. Interdiffusion of major elements at 1 atmosphere between natural shoshonitic and rhyolitic melts
  10. Factors controlling the crystal morphology and chemistry of garnet in skarn deposits: A case study from the Cuihongshan polymetallic deposit, Lesser Xing’an Range, NE China
  11. Gasparite-(La), La(AsO4), a new mineral from Mn ores of the Ushkatyn-III deposit, Central Kazakhstan, and metamorphic rocks of the Wanni glacier, Switzerland
  12. Cation ordering, valence states, and symmetry breaking in the crystal-chemically complex mineral chevkinite-(Ce): Recrystallization, transformation, and metamict states in chevkinite
  13. Discrete Zr and REE mineralization of the Baerzhe rare-metal deposit, China
  14. Origin of Monte Rosa whiteschist from in-situ tourmaline and quartz oxygen isotope analysis by SIMS using new tourmaline reference materials
  15. Chenmingite, FeCr2O4 in the CaFe2O4-type structure, a shock-induced, high-pressure mineral in the Tissint martian meteorite
  16. Letter
  17. Single-crystal elasticity of iron-bearing phase E and seismic detection of water in Earth’s upper mantle
  18. Book Review
  19. Book Review
https://doi.org/10.2138/am-2019-7015
Keywords for this article
Calcite; morphology, phosphate; phase transformation; fabrication; calcium carbonate; Biomaterials—Mineralogy Meets Medicine

Articles in the same Issue

  1. Carbonation and the Urey reaction
  2. Carbonation and decarbonation reactions: Implications for planetary habitability
  3. PO4 adsorption on the calcite surface modulates calcite formation and crystal size
  4. High-pressure Raman and Nd3+ luminescence spectroscopy of bastnäsite-(REE)CO3F
  5. Precipitates of α-cristobalite and silicate glass in UHP clinopyroxene from a Bohemian Massif eclogite
  6. Solubility behavior of δ-AlOOH and ɛ-FeOOH at high pressures
  7. Analyst and etching protocol effects on the reproducibility of apatite confined fission-track length measurement, and ambient-temperature annealing at decadal timescales
  8. Identification of interstratified mica and pyrophyllite monolayers within chlorite using advanced scanning/transmission electron microscopy
  9. Interdiffusion of major elements at 1 atmosphere between natural shoshonitic and rhyolitic melts
  10. Factors controlling the crystal morphology and chemistry of garnet in skarn deposits: A case study from the Cuihongshan polymetallic deposit, Lesser Xing’an Range, NE China
  11. Gasparite-(La), La(AsO4), a new mineral from Mn ores of the Ushkatyn-III deposit, Central Kazakhstan, and metamorphic rocks of the Wanni glacier, Switzerland
  12. Cation ordering, valence states, and symmetry breaking in the crystal-chemically complex mineral chevkinite-(Ce): Recrystallization, transformation, and metamict states in chevkinite
  13. Discrete Zr and REE mineralization of the Baerzhe rare-metal deposit, China
  14. Origin of Monte Rosa whiteschist from in-situ tourmaline and quartz oxygen isotope analysis by SIMS using new tourmaline reference materials
  15. Chenmingite, FeCr2O4 in the CaFe2O4-type structure, a shock-induced, high-pressure mineral in the Tissint martian meteorite
  16. Letter
  17. Single-crystal elasticity of iron-bearing phase E and seismic detection of water in Earth’s upper mantle
  18. Book Review
  19. Book Review
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