Skip to main content Accessibility help
×
Home

Characterization of smectite and illite by FTIR spectroscopy of interlayer NH4 + cations

  • J . Pironon (a1), M. Pelletier (a2), P. De Donato (a2) and R. Mosser-Ruck (a1)

Abstract

FTIR spectroscopy has been applied to NH4 +-exchanged dioctahedral clay minerals to determine the molecular environment of NH4 + and to quantify N concentration. FTIR under vapourpressure control, coupled with heating and freezing treatments has shown that NH4 + ion symmetry varies with the nature of clay minerals. NH4 + has a perfect tetrahedral symmetry in hydrated or dehydrated smectites and belongs to the T d symmetry group. The NH4 +-bending vibration is centred at 1450 and 1425 cm–1.

The Si4+-Al3+ substitution in dioctahedral clay minerals induces the loss of symmetry elements of the NH4 + tetrahedron which acquires a C 2v symmetry. As a consequence, the Td –C2v transition can be used to characterize the smectite–illite transition. Quantification of NH4 + content per half unit cell is provided by n NH4 = k[NH4]/[OH] where [NH4]/[OH] is the band area ratio of the NH4 +-bending vibration to the OH-stretching vibration. k = 1.1 for hydrated smectite, 0.9 for dehydrated smectite and 0.8 for illite or tobelite. The bending vibration of NH4 + is chosen for the calculation because it is not affected by superimposed contributions.

Copyright

Corresponding author

*E-mail: jacques.pironon@g2r.uhp-nancy.fr

References

Hide All
Barth, T., Rist, K., Huseby, B. & Ocampo, R. (1996) The distribution of nitrogen between bitumen, water and residue in hydrous pyrolysis of extracted Messel oil shale. Organic Geochemistry, 24, 889895.
Bastoul, A.M., Pironon, J., Mosbah, M., Dubois, M. & Cuney, M. (1993) In-situ analysis of nitrogen in minerals. European Journal of Mineralogy, 5, 233243.
Bérend, I., Cases, J.M., François, M., Uriot, J.P., Michot, L., Masion, A. & Thomas, F. (1995) Mechanism of adsorption and desorption of water vapor by homoionic montmorillonites: 2. The Li+, Na+, K+, Rb+ and Cs+-exchanged forms. Clays and Clay Minerals, 43, 324336.
Bishop, J.L., Pieters, C.M. & Edwards, J.O. (1994) Infrared spectroscopic analyses on the nature of water in montmorillonite. Clays and Clay Minerals, 42, 702716.
Bos, A., Duit, W., Van Der Eerden, A.M.J. & Jansen, B.H. (1988) Nitrogen storage in biotite: An experimental study of the ammonium and potassium partitioning between 1M-phlogopit e and vapour at 2 kb. Geochimica et Cosmochimica Acta, 52, 12751283.
Boudou, J.P., Mariotti, A. & Oudin, J.L. (1984) Unexpected enrichment of nitrogen during the diagenetic evolution of sedimentary organic matter. Fuel, 63, 15081510.
Casal, B., Ruiz-Hitzky, E. & Serratosa, J.M. (1984) Vibrational spectra of ammonium ions in crownether- NH4 +-montmorillonite complexes. Journal of the Chemical Society, Faraday Transactions 1, 80, 22252232.
Chourabi, B. & Fripiat, J.J. (1981) Determination of tetrahedral substitutions and interlayer surface heterogeneity from vibrational spectra of ammonium in smectites. Clays and Clay Minerals, 29, 260268.
Eypert-Blaison, C., Sauzéat, E., Pelletier, M., Michot, L.J., Villiéras, F. & Humbert, B. (2001) Hydration mechanism and swelling behavior of Na-magadiite. Chemistry of Materials, 13, 14801486.
Grishina, S., Pironon, J., Mazurov, M., Goryainov, S., Pustilnikov, A., Fon-der-Flaas, G. & Guerci, A. (1998) Organic inclusions in salt. Part 3: Oil and gas inclusions in Cambrian evaporite deposit (East Siberia). A contribution to the understanding of nitrogen generation. Organic Geochemistry, 28, 297310.
Herzberg, G. (1947) IR and Raman Spectra. II Polyatomic molecules. Van Nostrand, New York.
Higashi, S. (1982) Tobelite, a new ammonium dioctahedral mica. Mineralogical Journal, 11, 138146.
Higashi, S. (2000) Ammonium-bearing mica and mica/ smectite of several pottery stone and pyrophyllite deposits in Japan: their mineralogical properties and utilization. Applied Clay Science, 16, 171184.
Hunt, J.M. (1979) How gas forms. Pp. 150185 in Petroleum Geochemistry and Geology . Freeman & Co., San Francisco.
Lindgreen, H. (1994) Ammonium fixation during illitesmectite diagenesis in Upper Jurassic shale, North Sea. Clay Minerals, 29, 527537.
Morgan, H.W., Staats, P.A. & Goldstein, J.H. (1957) Infrared spectra of N15H3 and N15H4 + . Journal of Chemical Physics, 27, 1212.
Mortland, M.M., Fripiat, J.J., Chaussidon, J. & Uytterhoeven, J. (1963) Interaction between ammonia and the expanding lattices of montmorillonite and vermiculite. Journal of Physical Chemistry, 67, 248258.
Nakamoto, K. (1963) Infrared Spectra of Inorganic and Coordination Compounds, 2nd edition. Wiley, New York.
Pelletier, M., De Donato, P., Thomas, F., Michot, L. & Cases, J.M. (1999) Infrared spectroscopic study of water vapor adsorption by homoionic montmorillonites. The bending mode. Pp. 555560 in: Clays for our Future, Proceedings of the 11th International Clay Conference (Kodama, H., Mermut, A.R. & Torrance, J.C., editors). Ottawa, Canada, 1997. Published by ICC97 Organizing Committee, Ottawa, Canada.
Petit, S., Righi, D., Madejová, J. & Decarreau, A. (1999) Interpretation of the infrared NH4 + spectrum of the NH4 +-clays: application to the evaluation of the layer charge. Clay Minerals, 34, 543549.
Pironon, J., Pagel, M., Léveˆque, M.H. & Mogé, M. (1995a) Organic inclusions in salt: Part 1: Solid and liquid organic matter, carbon dioxide and nitrogen species in fluid inclusions from the Bresse Basin (France). Organic Geochemistry, 23, 391402.
Pironon, J., Pagel, M., Walgenwitz, F. & Barrès, O. (1995b) Organic inclusions in salt: Part 2: Oil, gas and ammonium in inclusions from the Gabon margin. Organic Geochemistry, 23, 739750.
Schroeder, P.A. & Ingall, E.D. (1994) A method for the determination of nitrogen in clays, with application to the burial diagenesis of shales. Journal of Sedimentary Research, A64, 694697.
Schroeder, P.A. & McLain, A.A. (1998) Illite-smectites and the influence of burial diagenesis on the geochemical cycling of nitrogen. Clay Minerals, 33, 539546.
Shigorova, T.A. (1982) The possibility of determining the ammonium content of mica by IR spectroscopy. Translation from Geokhimiya, 3, 458462.
SÏ uchá, V., Kraus, I. & Madejová, J. (1994) Ammonium illite from anchimetamorphic shales associated with anthracite in the Zemplinicum of the western Carpathians. Clay Minerals, 29, 369377.
Tissot, B.P. & Welte, D.H. (1984) Petroleum Formation and Occurrence . Springer, Berlin.
Van der Marel, H.W. & Beutelspacher, H. (1976) Atlas of Infrared Spectroscopy of Clay Minerals and their Admixtures. Elsevier, .Amsterdam.
Vedder, W. (1965) Ammonium in muscovite. Geochimica et Cosmochimica Acta, 29, 221228.
Williams, L.B. & Ferrell, R.E. (1991) Ammonium substitution during maturation of organic matter. Clays and Clay Minerals, 39, 400408.
Williams, L.B., Ferrell, R.E. Jr., Chinn, E.W. & Sassen, R. (1989) Fixed-ammonium in clays associated with crude oils. Applied Geochemistry, 4, 605616.

Keywords

Characterization of smectite and illite by FTIR spectroscopy of interlayer NH4 + cations

  • J . Pironon (a1), M. Pelletier (a2), P. De Donato (a2) and R. Mosser-Ruck (a1)

Metrics

Full text views

Total number of HTML views: 0
Total number of PDF views: 0 *
Loading metrics...

Abstract views

Total abstract views: 0 *
Loading metrics...

* Views captured on Cambridge Core between <date>. This data will be updated every 24 hours.

Usage data cannot currently be displayed