Hostname: page-component-848d4c4894-hfldf Total loading time: 0 Render date: 2024-04-30T21:59:36.962Z Has data issue: false hasContentIssue false
  • English
  • Français

A 19F Nuclear Magnetic Resonance Study of Natural Clays

Published online by Cambridge University Press:  28 February 2024

Andrea Labouriau ,
Yong-Wah Kim ,
Steve Chipera ,
David L. Bish  and
William L. Earl
Andrea Labouriau
Affiliation:
Chemical Sciences and Technology and Earth and Environmental Sciences Divisions, Los Alamos National Laboratory, Los Alamos, New Mexico 87545, U.S.A.
Yong-Wah Kim
Affiliation:
Chemical Sciences and Technology and Earth and Environmental Sciences Divisions, Los Alamos National Laboratory, Los Alamos, New Mexico 87545, U.S.A.
Steve Chipera
Affiliation:
Chemical Sciences and Technology and Earth and Environmental Sciences Divisions, Los Alamos National Laboratory, Los Alamos, New Mexico 87545, U.S.A.
David L. Bish
Affiliation:
Chemical Sciences and Technology and Earth and Environmental Sciences Divisions, Los Alamos National Laboratory, Los Alamos, New Mexico 87545, U.S.A.
William L. Earl
Affiliation:
Chemical Sciences and Technology and Earth and Environmental Sciences Divisions, Los Alamos National Laboratory, Los Alamos, New Mexico 87545, U.S.A.
Get access Rights & Permissions [Opens in a new window]

Abstract

A series of natural clays, including 1:1 layer silicates (serpentines, kaolin minerals), smectites, vermiculite, micas, talc, pyrophyllite, sepiolite, and palygorskite, were studied by 19F magic-angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy. The 19F chemical shift in these layer silicates is characteristic of the structure, in particular, to the local octahedral cation occupancy. Fluoride ions bonded to three Mg octahedral cations have a chemical shift of about −177 ppm and those bonded to two Al cations and a vacancy have a chemical shift of about −134 parts per million (ppm). The shift at −182.8 ppm in hectorite is apparently associated with fluoride bonded to two Al cations and a Li cation. Surprisingly, the difference in chemical shift of the interlayer and inner fluoride in 1:1 layer silicates is insufficient to distinguish these sites. Based on trends in chemical shift, it appears that fluoride substitution for inner hydroxyls in clays with octahedral substitution is not random. Fluoride is apparently preferentially associated with Mg rather than Al in the octahedral sheet as no resonance due to a fluoride bonded to two Al cations and a vacancy is observed in clays such as SAz-1.

Keywords

27AlAluminumClay minerals19FFluorineMASNMRSolid
Type
Research Article
Information
Clays and Clay Minerals , Volume 43 , Issue 6 , December 1995 , pp. 697 - 704
Copyright
Copyright © 1995, The Clay Minerals Society

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

Brindley, G. W., and Ertem, G. 1971. Preparation and solvation properties of some variable charge montmorillonites. Clays & Clay Miner. 19: 399–404.Google Scholar
Calvet, R., and Prost, R. 1971. Cation migration into empty octahedral sites and surface properties of clays. Clays & Clay Miner. 19: 175–186.Google Scholar
Clark, J. H., Goodman, E. M., Smith, D. K., Brown, S. J., and Miller, J. M. 1986. High resolution solid state 19F NMR spectroscopy as a tool for the study of ionic fluorides. J. Chem. Soc, Chem. Comm. 657–660.Google Scholar
Costanzo, P. M., Clemency, C. V., and Giese, R. F. 1980. Low temperature synthesis of a 10A hydrate of kaolinite using dimethylsulfoxide and ammonium fluoride. Clays & Clay Miner. 28: 155–156.Google Scholar
Daniel, M. E., and Hood, W. C. 1975. Alteration of shale adjacent to the Knight orebody, Rosiclare, Illinois. Econ. Geol. 70: 1062–1069.Google Scholar
Engelhardt, G., and Michel, D. 1989. High-Resolution Solid-State NMR of Silicates and Zeolites. New York: John Wiley & Sons, 485 pp.Google Scholar
Fyfe, C. A., 1983. Solid-State NMR for Chemists. Guelph: CFC Press, 593 pp.Google Scholar
Greene-Kelly, R., 1955. Dehydration of the montmorillonite minerals. Mineral. Mag. 30: 604–615.Google Scholar
Grim, R. E., 1968. Clay Mineralogy. New York: McGraw-Hill Book Company, 596 pp.Google Scholar
Harris, R. K., and Jackson, P. 1991. High-resolution fluorine-19 magnetic resonance of solids. Chem. Rev. 91: 1427–1440.Google Scholar
Hofmann, U., and Klemen, R. 1950. Verlust der austausch-fahigkeit von lithiumionen an bentonit durch ehritzung. Z. Anorg. Allegem. Chem. 262: 95–99.Google Scholar
Huve, L., Delmotte, L., Martin, P., Dred, R. Le, Baron, J., and Saehr, D. 1992a. 19F MAS-NMR study of structural fluorine in some natural and synthetic 2: 1 layer silicates. Clays & Clay Miner. 40: 186–191.Google Scholar
Huve, L., Saehr, D., Delmotte, L., Baron, J., and Dred, R. Le. 1992b. Fluorine 19 nuclear magnetic resonance spectroscopy of fluorinated phyllosilicates and phyllogermanates. C. R. Acad. Sci. Ser. II 315: 545–549.Google Scholar
Jaynes, W. F., and Bigham, J. M. 1987. Charge reduction, octahedral charge, and lithium retention in heated, Li-saturated smectites. Clays & Clay Miner. 35: 440–448.Google Scholar
Kreinbrink, A. T., Sazavsky, C. D., Pyrz, J. W., Nelson, D.G.A., and Honkonen, R. S. 1990. Fast-magic-angle-spinning 19F NMR of inorganic fluorides and fluoridated apatitic surfaces. J. Magn. Reson. 88: 267–276.Google Scholar
Martin, M. L., Dulpuech, J. J., and Martin, G. J. 1980. Practical NMR Spectroscopy. London: Heyden, 460 pp.Google Scholar
Nayeem, A., and Yesinowski, J. P. 1988. Calculation of magic-angle spinning nuclear magnetic resonance spectra of paramagnetic solids. J. Chem. Phys. 89: 4600–4608.Google Scholar
Sanz, J., and Stone, W.E.E. 1979. NMR study of micas, II. Distribution of Fe2+, F–, and OH– in the octahedral sheet of phlogopites. Amer. Mineral. 64: 119–126.Google Scholar
Santaren, J., Sanz, J., and Ruiz-Hitzky, E. 1990. Structural fluorine in sepiolite. Clays & Clay Miner. 38: 63–68.Google Scholar
Stebbins, J. F., 1992. Nuclear magnetic resonance spectroscopy of geological materials. Mat. Res. Soc. Bull. May: 45–52.Google Scholar
Thomas, J. Jr., Glass, H. D., White, W. A., and Trandel, R. M. 1977. Fluoride content of clay minerals and argillaceous earth materials. Clays & Clay Miner. 25: 278–284.Google Scholar
van Olphen, H., and Fripiat, J. J. 1979. Data Handbook for Clay Materials and other Non-Metallic Minerals. Oxford: Pergamon Press, 346 pp.Google Scholar
Weiss, V. A., Mehler, A., Koch, G., and Hofman, U. 1956. Uber das anionenaustauschvermögen der tonmineralien. Z. Anorg. Allegem. Chem. 284: 247–271.Google Scholar
Woessner, D. A., 1989. Characterization of clay minerals by 27Al nuclear magnetic resonance spectroscopy. Amer. Mineral. 74: 203–215.Google Scholar