Hostname: page-component-586b7cd67f-gb8f7 Total loading time: 0 Render date: 2024-11-22T05:39:44.950Z Has data issue: false hasContentIssue false
  • English
  • Français

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: [email protected]
Get access Rights & Permissions [Opens in a new window]

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

Access options

Get access to the full version of this content by using one of the access options below. (Log in options will check for institutional or personal access. Content may require purchase if you do not have access.)

References

Anthony, J.W., Bideaux, R.A., Bladh, K.W. and Nichols, M.C. (2000) Handbook of Mineralogy Volume IV: Arsenates, Phosphates and Vanadates. Mineral Data Publishing, Tuscon, Arizona, USA.Google Scholar
Farmer, V.C. (editor) (1974) The Infrared Spectra of Minerals. Mineralogical Society Monograph 4, 539 pp.CrossRefGoogle Scholar
Gevork'yan, S.V. and Povarennykh, A.S. (1973) Vibrational spectra of some iron phosphate hydrates. Konstitutsiya i Svoistva Mineralov, 7, 92–99.Google Scholar
Gevork'yan, S.V. and Povarennykh, A.S. (1980) Characteristics of the IR spectra of water molecules incorporated into phosphate and arsenate structures. Mineralogicheskiy Zhurnal, 2, 29–36.Google Scholar
Griffith, W.P. (1970) Raman studies on rock-forming minerals. II. Minerals containing MO3, MO4, and MO6 groups. Journal of the Chemical Society, A, 286–291.CrossRefGoogle Scholar
Henderson, G.S., Black, P.M., Rodgers, K.A. and Rankin, P.C. (1984) New data on New Zealand vivianite and metavivianite. New Zealand Journal of Geology and Geophysics, 27, 367–378.Google Scholar
Hunt, G.R. (1977) Spectral signatures of particulate minerals in the visible and near infrared. Geophysics, 42, 501–513.CrossRefGoogle Scholar
Hunt, G.R., Salisbury, J.W. and Lenhoff, C.J. (1972) Visible and near-infrared spectra of minerals and rocks. V. Halides, phosphates, arsenates, vanadates, and borates. Modern Geology, 3, 121–132.Google Scholar
Melendres, C.A., Camillone, N., III and Tipton, T. (1989) Laser Raman spectroelectrochemical studies of anodic corrosion and film formation on iron in phosphate solutions. Electrochimica Acta, 34, 281–286.CrossRefGoogle Scholar
Omori, K. and Seki, T. (1960) Infrared study of some phosphate minerals. Ganseki Kobutsu Kosho Gakkaishi, 44, 7–13.Google Scholar
Piriou, B. and Poullen, J.F. (1984) Raman study of vivianite. Journal of Raman Spectroscopy, 15, 343–346.CrossRefGoogle Scholar
Piriou, B. and Poullen, J.F. (1987) Infrared study of the vibrational modes of water in vivianite. Bulletin de Mineralogie, 110, 697–710.CrossRefGoogle Scholar
Sitzia, R. (1966) Infrared spectra of some natural phosphates. Rendiconti Seminario della Facolta di Scienze, Universita di Cagliari, 36, 105–115.Google Scholar
Takagi, S., Mathew, M. and Brown, W.E. (1986) Crystal structures of bobierrite and synthetic Mg3(PO4)2.8H2O. American Mineralogist, 71, 1229–1233.Google Scholar
Wildner, M., Giester, G., Lengauer, C.L. and McCammon, C.A. (1996) Structure and crystal chemistry of vivianite-type compounds: crystal structures of erythrite and annabergite with a Mössbauer study of erythrite. European Journal of Mineralogy, 8, 187–192.CrossRefGoogle Scholar
Wolfe, C.W. (1940) Classification of minerals of the type A3(XO4)2.nH2O. American Mineralogist, 25, 738–754, 787–809.Google Scholar