『Abstract
Aragonite and calcite single crystals can be readily transformed
into polycrystalline hydroxyapatite pseudomorphs by hydrothermal
treatment in a (NH4)2HPO4 solution. Scanning electron microscopy of the
reaction products showed that the transformation of aragonite
to apatite is characterised by the formation of a sharp interface
between the two phases and by the development of intracrystalline
porosity in the hydroxyapatite phase. In addition, electron backscattered
diffraction (EBSD) imaging showed that the c-axis of apatite is
predominantly oriented perpendicular to the reaction front with
no crystallographic relationship to the aragonite lattice. However,
the Ca isotopic composition of the parent aragonite, measured
by thermal ionization mass spectrometry was inherited by the apatite
product.
Hydrothermal experiments conducted with use of phosphate solutions
prepared with water enriched in 18O (97%) further revealed
that the 18O from the solution is incorporated in the
product apatite, as measured by micro-Raman spectroscopy. Monitoring
the distribution of 18O with Raman spectroscopy was
possible because the incorporation of 18O in the PO4 group of apatite generates four new Raman bands
at 945.8, 932, 919.7 and 908.8 cm-1, in addition to
the ν1 (PO4) symmetric
stretching band of apatite located at 962 cm-1, which
can be assigned to four 18O-bearing PO4
species. The relative intensities of these bands reflect the 18O
content in the PO4 group of the apatite product.
By using equilibrated and non-equilibrated solutions, with respect
to the 18O distribution between aqueous phosphate and
water, we could show that the concentration of 18O
in the apatite product is linked to the degree of 18O
equilibration in the solution. The textural and chemical observations
are indicative of a coupled mechanism of aragonite dissolution
and apatite precipitation taking place at a moving reaction interface.』
1. Introduction
2. Materials and methods
2.1. Starting material
2.2. Hydrothermal experiments
2.3. Analytical methods
2.3.1. Scanning electron microscopy (SEM) and electron microprobe
(EMP)
2.3.2. X-ray diffraction (XRD)
2.3.3. Raman spectroscopy
2.3.4. Electron backscatter diffraction (EBSD)
2.4. Calcium isotope ratios
2.4.1. Aragonite by apatite replacement for investigation of
the Ca isotopic composition
2.4.2. Sample preparation and Ca isotope analysis
3. Results
3.1. Hydrothermal experiments - textural and chemical observations
3.2. The behavior of 18O during the replacement of
aragonite by apatite in 18O-enriched solution
3.3. Analyses of the calcium isotopic composition of the initial
aragonite and of the product of the replacement reaction
4. Discussion
4.1. Textural relationships, calcium isotopic compositions
and the mechanism of the replacement reaction
4.2. The use of 18O as a tracer for the replacement
reaction
5. Conclusion
Acknowledgements
References