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1 School of Earth, Atmospheric and Environmental Sciences (SEAES), University of
Manchester, Manchester M13 9PL, UK
2 Photon Science Department, STFC Daresbury Laboratory, Warrington WA4 4AD,
UK
3 ISIS, Rutherford Appleton Laboratory, Chilton, Didcot, OX11 0QX, UK
4 Colorado School of Mines, Golden, Colorado 80401, USA
* E-mail: michael.henderson{at}manchester.ac.uk
The chemical composition of the natural arsenate-apatite mineral
johnbaumite [nominally
Ca10(AsO4)6(OH)2] and its
alteration product hedyphane
[Ca4Pb6(AsO4)6Cl2] have
been determined by electron microprobe analysis and the structures of
johnbaumite and synthetic Sr-, Ba- and Pb-arsenate apatites have been studied
by As K-edge X-ray absorption spectroscopy and synchrotron X-ray
powder diffraction. All samples belong to the holosymmetric apatite space
group P63/m with As5+ substituted for
P5+ in the tetrahedral structural site. Johnbaumite contains small
amounts of F and Pb (
0.9 and
4.4 wt.% respectively) and hedyphane
has the ideal composition (formula given above); the compositions of these
coexisting phases define the two limbs of a solvus occurring between Ca- and
Pb-arsenate apatite end members. The unit-cell parameters and cation-oxygen
bond lengths for the arsenate apatites studied are discussed alongside
published data for end-member Ca-, Sr-, Ba- and Pb-phosphate apatite analogues
with (OH), F, Cl or Br as the anions at the centres of the channels in the
apatite structure. This discussion rationalizes the relationships between the
two structural sites A(1) and A(2) occupied by divalent
cations in terms of the size of the A-O polyhedra and the distortion
of the A(1)-O polyhedron as measured by the metaprism twist angle
[O(1)-A(1)-O(2) projected onto (001)].
KEYWORDS: Arsenate apatites, johnbaumite, X-ray structure determination, crystal chemistry
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