Abstract
We report the first application of 39K solid-state NMR to the study of tecto- and phyllosilicates. Under high field (11.7 Tesla) and with the application of a spin-echo sequence, informative 39K spectra can be obtained for several compounds of interest to the geologist and the agronomist. Tectosilicates and phyllosilicates can be distinguished from the uncorrected frequency (δCG) of the observed NMR peak. A series of montmorillonites submitted to increasing numbers of wetting and drying cycles was studied in order to discriminate between mobile and “fixed” forms of K+: when the spectra are run on hydrated samples, two different signals are observed corresponding to K+ in different hydration states, and NMR data can be correlated with the amount of exchangeable K+ measured by ion exchange. Thus, it appears that NMR can provide useful information on K fixation complementary to classical chemical methods.
Similar content being viewed by others
References
Alma N. C. M., Hays G. R., Samoson A. V., and Lippmaa E. T. (1984) Characterisation of synthetic dioctahedral clays by solid state silicon-29 and aluminum-27 nuclear magnetic spectroscopy: Anal. Chem. 56, 729–733.
Bank S., Bank J. F., and Ellis P. D. (1989) Solid state 113Cd nuclear magnetic resonance study of exchanged montmorillonites: J. Phys. Chem. 93, 4847–4855.
Barron P. F., Slade P., and Frost R. L. (1985) Ordering of aluminum in tetrahedral sites in mixed-layer 2:1 phyllosilicates by solid-state high resolution NMR: J. Phys. Chem. 89, 3880–3885.
Bastow T. J. and Stuart S. N. (1990) 14N and 39K nuclear quadrupole coupling in KNO3: Z. Naturforsch. 45a, 459–463.
Conard J. (1976) Structure of water and hydrogen-bonding on clays studied by 7Li and 1H resonance: Magn. Res. in Coll, and Interf. Sci., ACS Symp. Ser. 34, 85–96.
Engelhardt G. and Michel D. (1987) High Resolution Solid State NMR of Silicates and Zeolites: J. Wiley & Sons, Chichester, 192–193.
Gaultier, J-P. (1978) “Etude d’un mécanisme de fixation du potassium dans les sols: la réorganisation structurale de la montmorillonite. Application à la montmorillonite biionique K-Ca”: Thesis, University of Paris, 90 pp.
Hendricks S. B. and Teller E. (1942) X-ray interference in partially ordered lattices: J. Chem. Phys. 10, 147–167.
Herrero C. P., Sanz J., and Serratosa J. M. (1986) Tetrahedral cation ordering in layer silicates by 29Si NMR spectroscopy: Solid State Comm. 53(2), 151–154.
Hougardy J., Stone W. E. E., and Fripiat J. J. (1976) NMR study of adsorbed water. I. Molecular orientation and protonic motion in the two-layer hydrate of a Na-vermiculite: J. Chem. Phys. 64(9), 3840–3851.
Kadi-Hanifi M. (1980) Proton nuclear magnetic resonance studies of “one-layer” hydrates of oriented hectorites: Clays & Clay Minerals 28(1), 65–66.
Kinsey R. A., Kirkpatrick R. J., Hower J., Smith K. A., and Oldfield E. (1985) High resolution aluminum-27 and silicon-29 nuclear magnetic resonance spectroscopic study of layer silicates, including clay minerals: Amer. Mineral. 70, 537–548.
Kirkpatrick R. J. (1988) MAS-NMR spectroscopy of minerals and glasses, in Reviews in Mineralogy, 18, F. C. Hawthorne, ed., The Mineralogical Society of America, 340–429.
Kunwar A. C., Turner G. L., and Oldfield E. J. (1986) Solid-state spin-echo Fourier transform NMR of 39K and 67Zn salts at high field: J. Magn. Res. 69, 124–127.
Laperche V., Lambert, J-F., Prost R., and Fripiat J. J. (1990) High resolution solid-state NMR of exchangeable cations on the interlayer surface of a swelling mica: 23Na, 111Cd and 133Cs-vermiculites: J.Phys. Chem. 94, 8821–8831.
Lipsicas M., Raythatha R. H., Pinnavaia T. J., Johnson I. J., Giese R. F., Jr., Costanzo P. M., and Robert J-L. (1984) Silicon and aluminum site distributions in 2:1 layered silicate clays: Nature 309, 604–607.
Lipsicas M., Straley C., Costanzo P. M., and Giese R. F., Jr. (1985) Static and dynamic structures of water in hydrated kaolinites: J. Colloid Interface Sci. 107(1), 221–230.
Luca V., Cardile C. M., and Meinhold R. H. (1989) High resolution multinuclear NMR study of cation migration in montmorillonite: Clay Miner. 24, 115–119.
Mamy J. (1968) Recherches sur l’hydratation de la montmorillonite: propriétés diélectriques et structure du film d’eau: Thesis, University of Paris, 113 pp.
Mamy J. and Gaultier, J-P. (1975) Etude de l’évolution de l’ordre cristallin dans la montmorillonite en relation avec la diminution d’échangeabilité du potassium, in Proc. Int. Clay Conf, Mexico City, 1975, S. W. Bailey, ed., Applied Publishing Ltd., 149–155.
Mamy J. and Gaultier, J-P. (1976) Les phénomènes de diffraction des rayonnements X et électroniques par les réseaux atomiques; application à l’étude de l’ordre cristallin dans les minéraux argileux—II. Evolution structurale de la montmorillonite associée au phénomène de fixation irréversible du potassium: Ann. Agron. 27(1), 1–16.
Plançon A., Besson G., Gaultier, J-P., Mamy J., and Tchoubar C. (1978) Qualitative and quantitative study of a structural reorganisation in montmorillonite after potassium fixation: in Proc. Int. Clay Conf, Oxford, 1978, M. M. Mortland and V. C. Farmer, eds., Elsevier, Amsterdam, 45–54.
Sanz J. and Serratosa J. M. (1984a) 29Si and 27Al high resolution MAS NMR spectra of phyllosilicates: J. Amer. Chem. Soc. 106, 4790–4793.
Sanz J. and Serratosa J. M. (1984b) Distinction of tetrahedrally and octahedrally coordinated Al in phyllosilicates by NMR spectroscopy: Clay Miner. 19, 113–115.
Schmidt V. H. (1971) Pulse response in the presence of quadrupolar splitting: in Lecture Notes, Ampere Summer School II, Yugoslavia 1971, R. Blinc, ed., Ljubljana, 75–81.
Soma M., Tanaka A., Seyama H., Hayashi S., and Hayaizaka K. (1989) Bonding states of sodium in tetrasilicic sodium fluoride micas: in Preprints of the 9th Int. Clay Conf, Strasbourg, 1989, 365 (poster session—abstract 224).
Taylor P. C., Baugher J. F., and Kriz H. M. (1975) Magnetic resonance spectra in polycrystalline solids: Chem. Rev. 75, 203–241.
Thompson J. G. (1984) 29Si and27Al nuclear magnetic resonance spectroscopy of 2:1 clay minerals: Clay Miner. 19, 229–236.
Tinet D., Faugère M. P., and Prost R. (1991) 113Cd N.M.R. chemical shift tensor analysis of cadmium-exchanged clays and clay gels: J. Phys. Chem. (in press).
Weiss C. A., Jr., Altaner S. P., and Kirkpatrick R. J. (1987) High resolution 29Si NMR spectroscopy of 2:1 layer silicates: Correlations among chemical shift, structural distortions, and chemical variations: Amer. Mineral. 72, 935–942.
Weiss C. A., Jr., Altaner S. P., and Kirkpatrick R. J. (1990) The structural environment of cations adsorbed onto clays: 133Cs variable temperature MAS-NMR spectroscopic study of hectorite: Geochim. Cosmochim. Acta 54, 1655–1669.
Woessner D. E. (1979) An NMR investigation into the range of the surface effects on the rotation of water: J. Magn. Res. 39, 297–308.
Woessner D. E. (1989) Characterisation of clay minerals by 27Al nuclear magnetic resonance spectroscopy: Amer. Mineral. 74, 203–215.
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Lambert, JF., Prost, R. & Smith, M.E. 39K Solid-State NMR Studies of Potassium Tecto- and Phyllosilicates: The In Situ Detection of Hydratable K+ in Smectites. Clays Clay Miner. 40, 253–261 (1992). https://doi.org/10.1346/CCMN.1992.0400301
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1346/CCMN.1992.0400301