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Solid-state 27Al and 29Si NMR analysis of hydroxy-Cr and-Al interlayered montmorillonite

Published online by Cambridge University Press:  09 July 2018

W. E. Dubbin
Affiliation:
Department of Soil Science, University of Manitoba, Winnipeg, Manitoba, MB R3T 2N2, Canada
Tee Boon Goh
Affiliation:
Department of Soil Science, University of Manitoba, Winnipeg, Manitoba, MB R3T 2N2, Canada

Abstract

The ease with which sorbed Cr(III) is released to solution via oxidation or cation exchange depends on its mode of complexation and the broader chemical environment in which it is held. This study was conducted to elucidate the chemical environment of hydrolysed Cr(III) sorbed onto montmorillonite, both alone and coprecipitated with Al. The 27Al MAS NMR revealed that Cr in the coprecipitated hydroxy interlayer created a second environment for AI, slightly more shielded than that of Al in the montmorillonite 2:1 layer. This observation is evidence for the presence of numerous Al-O-Cr linkages, thus revealing a uniform distribution of Al and Cr within the hydroxy polymers. The 29Si MAS NMR revealed a second environment for Si in the tetrahedral sheet of the Cr clays. This environment could be created only through a redistribution of electrons at the siloxane surface caused by inner-sphere complexation of Cr(III). Due to this inner-sphere complexation, sorbed Cr(III) is difficult to displace via simple exchange reactions and, consequently, its bioavailability is decreased.

Type
Research Article
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 1997

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References

Carr, R.M. (1985) Hydration states of interlametlar chromium ions in montmorillonite. Clays Clay Miner. 33, 357361.CrossRefGoogle Scholar
Cary, E.E., Allaway, W.H. & Olson, O.E. (1977) Control of chromium concentrations in food plants, 2. Chemistry of chromium in soils and its availability to plants. J. Agric. Food Chem. 25, 305309.CrossRefGoogle Scholar
Drljaca, A., Anderson, J.R., Spiccia, L. & Turney, T.W. (1992) Intercalation of montmorillonite with individual chromium(Ill) hydrolytic oligomers. Inorg. Chem. 31, 48944897.CrossRefGoogle Scholar
Dubbin, W.E. & Goh Tee Boon (1995) Sorptive capacity of montmorillonite for hydroxy-Cr polymers and the mode of Cr complexation. Clay Miner. 30, 175–185.CrossRefGoogle Scholar
Dubbin, W.E., Goh Tee Boon, Oscarson, D.W. & Hawthorne, F.C. (1994) Properties of hydroxy-A1 and -Cr interlayers in montmorillonite. Clays Clay Miner. 42, 331336.CrossRefGoogle Scholar
Fendorf, S.E., Lamble, G.M., Stapleton, M.G., Kelley, M.J. & Sparks, D.L. (1994) Mechanisms of chromium(Ill) sorption on silica. 1. Cr(III) surface structure derived by extended X-ray absorption fine structure spectroscopy. Environ. Sci. Technol. 28, 284289.CrossRefGoogle Scholar
Fendorf, S.E. & Sparks, D.L. (1994) Mechanisms of chromium(III) sorption on silica. 2. Effect of reaction conditions. Environ. Sci. Technol. 28, 290297.CrossRefGoogle ScholarPubMed
Goodman, B.A. & Stucki, J.W. (1984) The use of nuclear magnetic resonance (NMR) for the determination of tetrahedral aluminium in montmorillonite. Clay Miner. 19, 663667.Google Scholar
Grim, R.E. (1968) Clay Mineralogy. 2nd ed. McGraw-Hill, New York, NY.Google Scholar
Grove, J.H. & Ellis, B.G. (1980) Extractable chromium as related to soil pH and applied chromium. Soil Sci. Soc. Am. J. 44, 238242.CrossRefGoogle Scholar
Kinsey, R.A., Kirkpatrick, R.J., Hower, J., Smith, K.A. & Oldfield, E. (1985) High resolution aluminum-27 and silicon-29 nuclear magnetic resonance spectroscopic study of layer silicates, including clay minerals. Am. Miner. 70, 537548.Google Scholar
Kirkpatrick, R.J. (1988) MAS NMR spectroscopy of minerals and glasses. Pp. 341–403 in: Spectroscopic Methods in Mineralogy and Geology, Reviews in Mineralogy 18, (Hawthorne, F.C., editor). Mineralogical Society of America, Washington, DC.Google Scholar
Liang, J.-J. & Sherriff, B.L. (1993) Lead exchange into zeolite and clay minerals: A 29Si, 27Al, 23Na solidstate NMR study. Geochim. Cosmochim. Acta. 57, 38853894.Google Scholar
Malla, P.B. & Komarneni, S. (1993) Properties and characterization of Al2O3 and SiO2-TiO2 pillared saponite. Clays Clay Miner. 41, 472483.CrossRefGoogle Scholar
Morris, H.D., Bank, S. & Ellis, P.D. (1990) 27Al NMR spectroscopy of iron-bearing montmorillonite clays. J. Phys. Chem. 94, 31213129.Google Scholar
Oestrike, R., Yang, W.-H., Kirkpatrick, R.J., Hervig, R.L., Navrotsky, A. & Montez, B. (1987) High-resolution 23Na, 27Al, and 29Si NMR spectroscopy of framework aluminosilicate glasses. Geochim. Cosmochim. Acta. 51, 21992209.CrossRefGoogle Scholar
Oldfield, E., Kinsey, R.A., Smith, K.A., Nichols, J.A. & Kirkpatrick, R.J. (1983) High-resolution NMR of inorganic solids. Influence of magnetic centers on magic-angle sample-spinning lineshapes in some natural aluminosilicates. J. Magn. Res. 51, 325–329.Google Scholar
Paustenbach, D.J., Rinehart, W.E. & Sheehan, P.J. (1991) The health hazards posed by chromium-contaminated soils in residential and industrial areas: conclusions of an expert panel. Regul. Toxicol. Pharmacol. 13, 195222.CrossRefGoogle ScholarPubMed
Plee, D., Borg, L., Gatineau, L. & Fripiat, J.J. (1985) High resolution solid state 27A1 and e9si nuclear magnetic resonance study of pillared clay. J. Am. Chem. Soc. 107, 23622369.Google Scholar
Sanz, J. & Serratosa, J.M. (1984) 29Si and 27Al highresolution MAS-NMR spectra of phyllosilicates. J. Am. Chem. Soc. 106, 47904793.Google Scholar
Sheehan, P.J., Meyer, D.M., Sauer, M.M. & Paustenbach, D.J. (1991) Assessment of the human health risks posed by exposure to chromium-contaminated soils. J. Toxicol. Environ. Health. 32, 161201.Google Scholar
Sherriff, B.L. & Hartman, J.S. (1985) Solid-state highresolution 29Si NMR of feldspars: AI-Si disorder and the effects of paramagnetic centres. Can. Miner. 23, 205212.Google Scholar
Shewry, P.R. & Peterson, P.J. (1976) Distribution of chromium and nickel in plants and soil from serpentine and other sites. J. Ecol. 64, 195–212.CrossRefGoogle Scholar
van Olphen, H. & Fripiat, J.J. (1979) Data Handbook for Clay Materials and other Non-metallic Minerals. Pergamon Press, Toronto.Google Scholar
Weaver, C.E. & Pollard, L.D. (1973) Smectite. Pp. 55–86 in: The Chemistry of Clay Minerals: Developments in Sedimentology. Vol. 15. Elsevier, Amsterdam.Google Scholar
Wilson, M.A., Barron, P.F. & Campbell, A.S. (1984) Detection of aluminium coordination in soils and clay fractions using 27A1 magic angle spinning n.m.r. J. Soil Sci. 35, 201207.Google Scholar
Woessner, D.E. (1989) Characterization of clay minerals by 27Al nuclear magnetic resonance spectroscopy. Am. Miner. 74, 203215.Google Scholar