DOI: 10.1180/0026461026660077. Raman and infrared spectroscopic study of the vivianite-group phosphates vivianite, baricite and bobierrite

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

10.1180/0026461026660077

Crossref journal-article

Mineralogical Society

Mineralogical Magazine (7149)

Abstract

AbstractThe 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.

Bibliography

Frost, R. L., Martens, W., Williams, P. A., & Kloprogge, J. T. (2002). Raman and infrared spectroscopic study of the vivianite-group phosphates vivianite, baricite and bobierrite. Mineralogical Magazine, 66(6), 1063â1073.

Authors 4

R. L. Frost (first)
W. Martens (additional)
P. A. Williams (additional)
J. T. Kloprogge (additional)

References 16 Referenced 171

{'key': 'S0026461X00045308_ref3', 'first-page': '92', 'article-title': 'Vibrational spectra of some iron phosphate hydrates', 'volume': '7', 'author': "Gevork'yan", 'year': '1973', 'journal-title': 'Konstitutsiya i Svoistva Mineralov'} / Konstitutsiya i Svoistva Mineralov / Vibrational spectra of some iron phosphate hydrates by Gevork'yan (1973)
{'key': 'S0026461X00045308_ref10', 'first-page': '7', 'article-title': 'Infrared study of some phosphate minerals', 'volume': '44', 'author': 'Omori', 'year': '1960', 'journal-title': 'Ganseki Kobutsu Kosho Gakkaishi'} / Ganseki Kobutsu Kosho Gakkaishi / Infrared study of some phosphate minerals by Omori (1960)
{'key': 'S0026461X00045308_ref16', 'first-page': '738', 'article-title': 'Classification of minerals of the type A3(XO4)2.nH2O', 'volume': '25', 'author': 'Wolfe', 'year': '1940', 'journal-title': 'American Mineralogist'} / American Mineralogist / Classification of minerals of the type A3(XO4)2.nH2O by Wolfe (1940)
10.1002/jrs.1250150510
{'key': 'S0026461X00045308_ref14', 'first-page': '1229', 'article-title': 'Crystal structures of bobierrite and synthetic Mg3(PO4)2.8H2O', 'volume': '71', 'author': 'Takagi', 'year': '1986', 'journal-title': 'American Mineralogist'} / American Mineralogist / Crystal structures of bobierrite and synthetic Mg3(PO4)2.8H2O by Takagi (1986)
10.1039/j19700000286
{'key': 'S0026461X00045308_ref13', 'first-page': '105', 'article-title': 'Infrared spectra of some natural phosphates', 'volume': '36', 'author': 'Sitzia', 'year': '1966', 'journal-title': 'Rendiconti Seminario della Facolta di Scienze, Universita di Cagliari'} / Rendiconti Seminario della Facolta di Scienze, Universita di Cagliari / Infrared spectra of some natural phosphates by Sitzia (1966)
{'volume-title': 'Handbook of Mineralogy Volume IV: Arsenates, Phosphates and Vanadates.', 'year': '2000', 'author': 'Anthony', 'key': 'S0026461X00045308_ref1'} / Handbook of Mineralogy Volume IV: Arsenates, Phosphates and Vanadates. by Anthony (2000)
10.1016/0013-4686(89)87098-7
{'key': 'S0026461X00045308_ref6', 'first-page': '367', 'article-title': 'New data on New Zealand vivianite and metavivianite', 'volume': '27', 'author': 'Henderson', 'year': '1984', 'journal-title': 'New Zealand Journal of Geology and Geophysics'} / New Zealand Journal of Geology and Geophysics / New data on New Zealand vivianite and metavivianite by Henderson (1984)
10.1190/1.1440721
10.1127/ejm/8/1/0187
{'key': 'S0026461X00045308_ref8', 'first-page': '121', 'article-title': 'Visible and near-infrared spectra of minerals and rocks. V. Halides, phosphates, arsenates, vanadates, and borates', 'volume': '3', 'author': 'Hunt', 'year': '1972', 'journal-title': 'Modern Geology'} / Modern Geology / Visible and near-infrared spectra of minerals and rocks. V. Halides, phosphates, arsenates, vanadates, and borates by Hunt (1972)
10.3406/bulmi.1987.8013
{'key': 'S0026461X00045308_ref4', 'first-page': '29', 'article-title': 'Characteristics of the IR spectra of water molecules incorporated into phosphate and arsenate structures', 'volume': '2', 'author': "Gevork'yan", 'year': '1980', 'journal-title': 'Mineralogicheskiy Zhurnal'} / Mineralogicheskiy Zhurnal / Characteristics of the IR spectra of water molecules incorporated into phosphate and arsenate structures by Gevork'yan (1980)
10.1180/mono-4

Dates

Type	When
Created	21 years ago (Aug. 27, 2004, 11:27 p.m.)
Deposited	4 years, 6 months ago (Feb. 4, 2021, 3:53 a.m.)
Indexed	1 month ago (July 28, 2025, 5:58 p.m.)
Issued	22 years, 9 months ago (Dec. 1, 2002)
Published	22 years, 9 months ago (Dec. 1, 2002)
Published Online	7 years, 1 month ago (July 5, 2018)
Published Print	22 years, 9 months ago (Dec. 1, 2002)

Funders 0

None

BibTeX

@article{Frost_2002, title={Raman and infrared spectroscopic study of the vivianite-group phosphates vivianite, baricite and bobierrite}, volume={66}, ISSN={1471-8022}, url={http://dx.doi.org/10.1180/0026461026660077}, DOI={10.1180/0026461026660077}, number={6}, journal={Mineralogical Magazine}, publisher={Mineralogical Society}, author={Frost, R. L. and Martens, W. and Williams, P. A. and Kloprogge, J. T.}, year={2002}, month=dec, pages={1063–1073} }

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  "abstract": "<jats:title>Abstract</jats:title><jats:p>The molecular structure of the three vivianite-structure, compositionally related phosphate minerals vivianite, baricite and bobierrite of formula M<jats:sub>3</jats:sub><jats:sup>2+</jats:sup>(PO<jats:sub>4</jats:sub>)<jats:sub>2</jats:sub>.8H<jats:sub>2</jats:sub>O where <jats:italic>M</jats:italic> 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<jats:sup>\u22121</jats:sup> 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<jats:sup>\u22121</jats:sup> 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<jats:sup>\u22121</jats:sup> 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.</jats:p>",
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