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Raman and infrared spectroscopic study of the vivianite-group phosphates vivianite, baricite and bobierrite

Published online by Cambridge University Press:  05 July 2018

R. L. Frost ,
W. Martens ,
P. A. Williams  and
J. T. Kloprogge
R. L. Frost*
Affiliation:
Centre for Instrumental and Developmental Chemistry, Queensland University of Technology, GPO Box 2434, Brisbane Queensland 4001, Australia
W. Martens
Affiliation:
Centre for Instrumental and Developmental Chemistry, Queensland University of Technology, GPO Box 2434, Brisbane Queensland 4001, Australia
P. A. Williams
Affiliation:
School of Science, Food and Horticulture, University of Western Sydney, Locked Bag 1797, Penrith South DC NSW 1797, Australia
J. T. Kloprogge
Affiliation:
Centre for Instrumental and Developmental Chemistry, Queensland University of Technology, GPO Box 2434, Brisbane Queensland 4001, Australia
*
*E-mail: r.frost@qut.edu.au
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Abstract

The molecular structure of the three vivianite-structure, compositionally related phosphate minerals vivianite, baricite and bobierrite of formula M32+(PO4)2.8H2O where M is Fe or Mg, has been assessed using a combination of Raman and infrared (IR) spectroscopy. The Raman spectra of the hydroxyl-stretching region are complex with overlapping broad bands. Hydroxyl stretching vibrations are identified at 3460, 3281, 3104 and 3012 cm−1 for vivianite. The high wavenumber band is attributed to the presence of FeOH groups. This complexity is reflected in the water HOH-bending modes where a strong IR band centred around 1660 cm−1 is found. Such a band reflects the strong hydrogen bonding of the water molecules to the phosphate anions in adjacent layers. Spectra show three distinct OH-bending bands fromstrongly hydrogen-bonded, weakly hydrogen bonded water and non-hydrogen bonded water. The Raman phosphate PO-stretching region shows strong similarity between the three minerals. In the IR spectra, complexity exists with multiple antisymmetric stretching vibrations observed, due to the reduced tetrahedral symmetry. This loss of degeneracy is also reflected in the bending modes. Strong IR bands around 800 cm−1 are attributed to water librational modes. The spectra of the three minerals display similarities due to their compositions and crystal structures, but sufficient subtle differences exist for the spectra to be useful in distinguishing the species.

Keywords

baricitebobierritevivianiteironphosphateRaman spectroscopyinfrared spectroscopy
Type
Research Article
Information
Mineralogical Magazine , Volume 66 , Issue 6 , December 2002 , pp. 1063 - 1073
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 2002

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