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Transition Metals in Llano Vermiculite Samples: An EPR Study

Published online by Cambridge University Press:  28 February 2024

P. M. Schosseler  and
A. U. Gehring
P. M. Schosseler
Affiliation:
Laboratory for Physical Chemistry, Swiss Federal Institute of Technology, ETH, CH-8092 Zürich, Switzerland
A. U. Gehring*
Affiliation:
Swiss Federal Institute for Forest, Snow and Landscape Research, WSL/ETH CH-8903 Birmensdorf, Switzerland
*
†Present address: Institute of Terrestrial Ecology ETH Zurich Grabenstrasse 3 CH 8952 Schlieren Switzerland.
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Abstract

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Continuous wave and pulsed electron paramagnetic resonance spectroscopies combined with thermal and chemical methods were used to identify and characterize V(TV), Fe(III), Mn(II) and Cr(III) in a multimineral system that consists of vermiculite and impurities of carbonates. All of these transition metals were structure-bound in mineral phases. The V(IV) was located in octahedral layers of the vermiculite and became oxidized to V(V) during the transformation of the host mineral to enstatite at about 800 °C. The Fe(III) was associated with the vermiculite as well as the carbonate impurities. The Fe(III) identified in the vermiculite was transferred into the enstatite structure during the thermal conversion. An indirect proof of Fe(III) and Cr(III) in the impurities was found in the heated samples in which these cations occurred in Ca and/or Mg oxides that were formed by transformation of the carbonates. The Mn(II) in the untreated samples was associated with the impurities and was also detected in oxides formed from the samples heated at 600 °C.

Keywords

CarbonatesCw and Pulsed Electron Paramagnetic Resonance SpectroscopiesPhase TransformationVermiculite
Type
Research Article
Information
Clays and Clay Minerals , Volume 44 , Issue 4 , August 1996 , pp. 470 - 478
Copyright
Copyright © 1996, The Clay Minerals Society

References

Angel, B.R. and Vincent, W.E.J.. 1978. Electron spin resonance studies of iron oxides associated with the surface of kaolins. Clays & Clay Miner 26: 263–272.CrossRefGoogle Scholar
Beltrán-Lòpez, V. and Castro-Tello, J.. 1980. ESR lineshapes in polycrystalline samples: 6S5/2 ions in axial and cubic crystal fields. J Magn Reson 39: 437–460.Google Scholar
Bilton, M.S., Gilson, T.R. and Webster, M.. 1972. The vibration spectra of some chain type silicate minerals. Spectrochim Acta 28A: 2113–2119.CrossRefGoogle Scholar
Butler, A.. 1990. The coordination and redox chemistry of vanadium in aqueous solutions. In: Chasteen, N.E., editor. Vanadium in biological systems. Dordrecht: Kluwer Academ Publ. p 25–49.CrossRefGoogle Scholar
Calas, G.. 1988. Electron paramagnetic resonance. In: Hawthorn, F.C., editor. Sprectroscopic methods in mineralogy and geology. Rev Miner 18: 513–571.CrossRefGoogle Scholar
Clabaugh, S.E. and Barnes, V.E.. 1959. Vermiculite in central Texas. Texas Univ Bur Econ Geol Rept Invest p 40–45.CrossRefGoogle Scholar
Dikanov, S.A. and Astahikin, A.V.. 1989. ESEEM of disordered systems: Theory and applications. In: Hoff, A.J., editor. Advanced EPR, applications in biology and biochemistry, Amsterdam: Elsevier. p 59–115.Google Scholar
Farmer, V.C.. 1974. The infrared spectra of minerals. London: Mineralogical Society. 539 p.CrossRefGoogle Scholar
Fauth, J.-M., Schweiger, A., Braunschweiler, L., Forrer, J. and Ernst, R.R.. 1986. Elimination of unwanted echoes and reduction of dead time in three-pulse electron spin-echo spectroscopy. J Magn Reson 66: 74–85.Google Scholar
Gehring, A.U. and Karthein, R.. 1990. An ESR and calorimetric study of iron oolitic samples from the Northampton ironstone. Clay Miner 25: 303–311.CrossRefGoogle Scholar
Gehring, A.U., Fry, I.V., Luster, J. and Sposito, G.. 1993a. Vanadium (IV) in a multimineral lateritic saprolite: A thermoanalytical and spectroscopic study. Soil Sci Soc Am J 57: 868–873.CrossRefGoogle Scholar
Gehring, A.U., Fry, I.V., Luster, J. and Sposito, G.. 1993b. The chemical form of vanadium(IV) in kaolinite. Clays & Clay Miner 41: 662–667.CrossRefGoogle Scholar
Gehring, A.U., Schosseler, P.M. and Luster, J.. 1994. The chemical form of Mn(II) and V(IV) in mineral phases as determined by EPR spectroscopy. Miner Mag 58A: 323–324.CrossRefGoogle Scholar
Gehring, A.U. and Sposito, G.. 1995. Residual manganese(II) speciation in montmorillonite: A reply. Clays & Clay Miner 43: 385–386.CrossRefGoogle Scholar
Herrero, C.P., Sanz, J. and Serratosa, J.M.. 1985. Si and Al distribution in micas: Analysis by high-resolution Si NMR spectroscopy. J Phys C, Solid State Phys 18: 13–22.CrossRefGoogle Scholar
Joint Committee on Powder Diffraction Standards (JCPDS). 1980. Mineral powder diffraction file, data book. Swarthmore, PN: JCPDS international center for diffraction data.Google Scholar
Jones, G.C. and Jackson, B.. 1992. Infrared transmission spectra of carbonate minerals. London: Chapman & Hall.Google Scholar
Jones, J.P.E., Angel, B.R. and Hall, P.L.. 1974. Electron spin resonance of synthetic kaolinite II. Clay Miner 10: 257—270.CrossRefGoogle Scholar
Karthein, R., Motschi, H., Schweiger, A., Ibric, S., Sulzberger, B. and Stumm, W.. 1991. Interaction of chromium(III) complexes with hydrous δ-Al2O3: Rearrangements in the coordination sphere studied by electron spin resonance and electron spin-echo spectroscopies. Inorg Chem 30: 1606–1611.CrossRefGoogle Scholar
Kevan, L.. 1979. Modulation of electron spin-echo decay in solids. In: Kevan, L., Schwartz, R.N., editors. Time domain electron spin resonance. New York: Wiley. p 279–341.Google Scholar
Lloyd, R.V., Morrison, J.W. and Lumsden, D.N.. 1993. The influence of ferrous and ferric iron on the Mn2+ partitioning ratio and ESR signal of synthetic dolomite. Geochim Cosmochim Acta 57: 1071–1078.CrossRefGoogle Scholar
Low, W.. 1957a. Paramagnetic resonance and optical absorption spectra of Cr3+ in MgO. Phys Rev 105: 801–805.CrossRefGoogle Scholar
Low, W.. 1957b. Paramagnetic resonance of manganese in cubic MgO and CaF2l. Phys Rev 105: 793–800.CrossRefGoogle Scholar
Mankowitz, J. and Low, W.. 1970. Forbidden transitions (Δm = ±1) in the paramagnetic resonance absorption of Mn2+ in calcite. Phys Rev B 2: 28–32.CrossRefGoogle Scholar
McBride, M.B.. 1990. Electron spin resonance spectroscopy. In: Perry, D.L., editor. Instrumental surface analysis of geological materials. New York: VCH Publ. p 233–281.Google Scholar
McBride, M.B.. 1995. Comment on the natural Mn(II) EPR signal of SWy-1 montmorillonite. Clays & Clay Miner 43: 383–384.CrossRefGoogle Scholar
Meads, R.E. and Malden, P.J.. 1975. Electron spin resonance in natural kaolinites containing Fe3+ and other transition metal ions. Clay Miner 10: 313–345.CrossRefGoogle Scholar
Mims, W.B.. 1972. Envelope modulation in spin-echo experiments. Phys Rev B 5: 2409–2419.CrossRefGoogle Scholar
Mims, W.B. and Peisach, J.. 1981. Electron spin echo spectroscopy and the study of metallproteins. In: Berliner, L.J., Reuben, J., editors. Biological magnetic resonance, Vol. 3. New York: Plenum. p 213–263.CrossRefGoogle Scholar
Möhl, W., Schweiger, A. and Motschi, H.. 1990. Modes of phosphate binding to copper(II): Investigation of the electron spin echo envelope modulation of complexes on surfaces and in solutions. Inorg Chem 29: 1536–1543.CrossRefGoogle Scholar
Olivier, D., Vedrine, J.C. and Pezerat, H.. 1975. Application de la résonance paramagnétique électronique à la localisation du Fe3+ dans les smectites. Bull Groupe Franç Argiles 27: 153–165.CrossRefGoogle Scholar
Schweiger, A.. 1991. Pulsed electron spin resonance spectroscopy: Basic principles, techniques, and examples of applications. Angew Chem Int Engl 30: 265–292.CrossRefGoogle Scholar
Suquet, H., Mallard, C., Quarton, M., Dubernat, J. and Perzerat, H.. 1984. Etude du biopyribole formé par chauffage des vermiculites magnésiennes. Clay Miner 19: 217–227.CrossRefGoogle Scholar
Suquet, H., Chevalier, S., Marcilly, C. and Barthomeuf, D.. 1991. Preparation of porous materials by chemical activation of the Llano vermiculite. Clay Miner 26: 49–60.CrossRefGoogle Scholar
Veblen, D.R.. 1991. Polysomatism and polysomatic series: A review and applications. Am Mineral 76: 801–826.Google Scholar
Veblen, D.R. and Buseck, P.. 1980. Microstructures and reaction mechanisms in biopyriboles. Am Mineral 65: 599–623.Google Scholar
Wildemann, T.R.. 1970. The distribution of Mn2+ in some carbonates by electron paramagnetic resonance. Chem Geol 5: 167–177.CrossRefGoogle Scholar