Clays and Clay Minerals

, Volume 35, Issue 1, pp 11–20 | Cite as

Effect of Manganese on the Transformation of Ferrihydrite into Goethite and Jacobsite in Alkaline Media

  • R. M. Cornell
  • R. Giovanoli


In the presence of Mn(II), ferrihydrite transforms into Mn-goethite and/or jacobsite. Chemical analysis showed that as much as 15 mole % Mn replaced Fe in the goethite structure. If Mn(III) replaced Mn(II), the formation of jacobsite was suppressed; ferrihydrite transformed into Mn-goethite, and, at high Mn(III) concentrations, a 7-Å phyllomanganate. Low levels of Mn(II) retarded the transformation of ferrihydrite only slightly, whereas in an Mn(III) system the nucleation and growth of Mn-goethite were both hindered. Mn-goethite nucleated in solution, whereas jacobsite appeared to form by interaction of dissolved Mn(II) species with ferrihydrite. Mn suppressed the formation of hematite in these systems; however, Mn-hematite containing as much as 5 mole % Mn was induced to form at pH 8 by adding oxalate to the system. Transmission electron micrographs showed that goethite crystals grown in the presence of Mn were long (≤2 μm) and thin and commonly contained etch pits. The presence of Mn appears to have promoted twinning.

Key Words

Ferrihydrite Goethite Jacobsite Manganese Phyllomanganate Synthesis Transmission electron microscopy 


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  1. Azaroff, L. V. (1960) Introduction to Solids: McGraw-Hill, New York, 460 pp.Google Scholar
  2. Cornell, R. M. (1985) Effect of simple sugars on the alkaline transformation of ferrihydrite into goethite and hematite: Clays & Clay Minerals 33, 219–227.CrossRefGoogle Scholar
  3. Cornell, R. M. and Giovanoli, R. (1985) Effect of solution conditions on the proportion and morphology of goethite formed from ferrihydrite: Clays & Clay Minerals 33, 424–432.CrossRefGoogle Scholar
  4. Cornell, R. M., Giovanoli, R., and Schindler, P. W. (1987) Effect of silicate species on the transformation of ferrihydrite into goethite and hematite in alkaline media: Clays & Clay Minerals 35, 21–28.CrossRefGoogle Scholar
  5. Cornell, R. M. and Schwertmann, U. (1979) Influence of organic anions on the crystallization of ferrihydrite: Clays & Clay Minerals 27, 402–410.CrossRefGoogle Scholar
  6. Davies, S. R. H. (1984) Mn(II) oxidation in the presence of metal oxides: Ph.D. thesis, California Institute of Technology, Pasadena, California, 170 pp.Google Scholar
  7. Feitknecht, W., Oswald, H. R., and Feitknecht-Steinmann, U. (1960) Über die Topochemische einphasige Reduktion von γ-MnO2: Helv. Chim. Acta 43, 1947–1950.CrossRefGoogle Scholar
  8. Fey, M. V. and Dixon, J. B. (1981) Synthesis and properties of poorly crystalline hydrated aluminous goethites: Clays & Clay Minerals 29, 91–100.CrossRefGoogle Scholar
  9. Fischer, W. R. and Schwertmann, U. (1975) The formation of hematite from amorphous iron(III) hydroxide: Clays & Clay Minerals 23, 33–37.CrossRefGoogle Scholar
  10. Giovanoli, R. (1976) Vom Hexaquo-Mangan zum Mangan Sediment. Reaktionsequenzen feinteiliger fester Manganoxidhydroxide: Chimia 30, 118–119.Google Scholar
  11. Giovanoli, R. and Stähli, E. (1970) Oxide und Oxyhydroxide des drei- und vierwertigen Mangans: Chimia 24, 40–52.Google Scholar
  12. Lewis, D. G. and Schwertmann, U. (1979) The influence of Al on iron oxides. Part III. Preparation of Al goethites in M KOH: Clay Miner. 14, 115–126.CrossRefGoogle Scholar
  13. Mann, S., Cornell, R. M., and Schwertmann, U. (1985) The influence of aluminium on iron oxides: XII. High resolution transmission electron microscopic (HRTEM) study of aluminous goethites: Clay Miner. 20, 255–262.CrossRefGoogle Scholar
  14. Parfitt, R. L., Farmer, V. C, and Russell, J. D. (1977) Adsorption on hydrous oxides. I. Oxalate and benzoate on goethite: J. Soil Sci. 28, 29–39.CrossRefGoogle Scholar
  15. Santschi, P. H. and Schindler, P. W. (1974) Complex formation in the ternary systems Ca2+-H4SiO4-H2O and Mg2+-H4SiO4-H2O: J. Chem. Soc. Dalton, 181–184.Google Scholar
  16. Schulze, D. G. (1984) The influence of aluminum on iron oxides. VIII. Unit-cell dimensions of Al-substituted goethites and estimation of Al from them: Clays & Clay Minerals 32, 36–44.CrossRefGoogle Scholar
  17. Schulze, D. G. and Schwertmann, U. (1984) The influence of aluminium on iron oxides: X. Properties of Al-substituted goethites: Clay Miner. 19, 521–539.CrossRefGoogle Scholar
  18. Schwertmann, U. (1964) Differenzierung der Eisenoxides des Bodens durch Extraktion mit einer Ammoniumoxalat-Lösung: Z. Pflanzenernähr. Düng Bodenkd. 105, 194–202.CrossRefGoogle Scholar
  19. Schwertmann, U. (1985) Effect of pedogenic environments on iron oxide minerals: Adv. Soil Sci. 1, 171–200.CrossRefGoogle Scholar
  20. Schwertmann, U., Fitzpatrick, R. W., Taylor, R. M., and Lewis, D. G. (1979) The influence of aluminum on iron oxides. Part II. Preparation and properties of Al-substituted hematites: Clays & Clay Minerals 27, 105–112.CrossRefGoogle Scholar
  21. Schwertmann, U. and Murad, E. (1983) The effect of pH on the formation of goethite and hematite from ferrihydrite: Clays & Clay Minerals 31, 277–284.CrossRefGoogle Scholar
  22. Shannon, R. D. and Prewitt, C. T. (1969) Effective ionic radii in oxides and fluorides: Acta Crystallogr. B25, 925–946.Google Scholar
  23. Stiers, W. and Schwertmann, U. (1985) Evidence for manganese substitution in synthetic goethite: Geochim. Cosmochim. Acta 49, 1909–1911.CrossRefGoogle Scholar
  24. Stumm, W. and Morgan, J. J. (1981) Aquatic Chemistry: 2nd ed., Wiley, New York, 780 pp.Google Scholar
  25. Tamaura, Y., Buduan, P. V., and Katsura, T. (1981) Studies in the oxidation of iron(II) ion during formation of Fe3O4 and α-FeOOH by air oxidation of Fe(OH)2 suspensions: J. Chem. Soc. Dalton, 1807–1811.Google Scholar
  26. Thiry, M. and Sornein, J. (1983) Pétrologie d’une séquence d’altération de carbonate de fer: Sci. Geol. Mem. 73, 195–205.Google Scholar
  27. Van Hook, H. J. and Keith, M. L. (1958) The system Fe3O4-Mn3O4: Amer. Mineral. 43, 69–83.Google Scholar

Copyright information

© The Clay Minerals Society 1987

Authors and Affiliations

  • R. M. Cornell
    • 1
  • R. Giovanoli
    • 2
  1. 1.Institute of Inorganic ChemistryUniversity of BerneBerne 9Switzerland
  2. 2.Laboratory of Electron MicroscopyUniversity of BerneBerne 9Switzerland

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