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Clays and Clay Minerals

, Volume 52, Issue 4, pp 462–472 | Cite as

Mineralogical characteristics and micromorphological observations of brittle/soft Fe/Mn concretions from Okinawan soils

  • L. P. Vidhana Arachchi
  • Y. TokashikiEmail author
  • S. Baba
Article

Abstract

Manganese minerals are not common and the distinction of poorly crystalline Mn minerals from other associated minerals is important. For many years, the crystal structures of poorly crystalline Mn minerals in Fe/Mn concretions have been the subject of considerable conjecture and controversy. This study reports the micromorphological and mineralogical characteristics, and the chemical composition of Fe/Mn minerals in soft Fe/Mn concretions formed in Shimajiri Mahji soils (Typic Hapludalfs) that developed from Ryukyu limestone on Okinawa Island, Japan. The Fe/Mn minerals in brittle/soft Fe/Mn concretions were characterized using a sequential selective dissolution procedure (SSDP) by treatments with NaOH, hydroxylamine hydrochloride (HAHC) at 25°C and 60°C, and dithionite-citrate-bicarbonate (DCB) in combination with X-ray diffraction (XRD) and scanning electron microscopy (SEM). The HAHC treatment at 25°C dissolved birnessite, but not lithiophorite and goethite. A subsequent extraction with HAHC at 60°C dissolved lithiophorite but not goethite. Finally, the DCB treatment was able to dissolve goethite. The SEM images show that birnessite crystals, with a blade- or plate-like habit, form globular aggregates inside veins and cavities. Pseudo-hexagonal crystals of lithiophorite have produced thread-ball structures with crystal shape similar to birnessite and birnessite crystals are closely associated with lithiophorite. Well developed hexagonal plates of gibbsite crystals are clustered in different directions to make foliated vermiform structures. Aggregates of goethite crystals are acicular and are arranged into stars. The supplementary SSDP, in combination with XRD and SEM techniques, provides methods to distinguish and partly quantify birnessite and lithiophorite in the presence of layer silicate and Fe oxide minerals and confirm their own morphological features.

Key Words

Chemical Composition Fe/Mn Minerals Layer Silicate Mineral Micromorphology SEM and XRD Techniques Sequential Selective Dissolution Procedure 

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References

  1. Barbara, A.C., Steve, J.C., David, L.B. and Sandra, J.C. (1993) Fracture-lining manganese oxide minerals in Silicic tuff, Yucca Mountain, Nevada, U.S.A. Chemical Geology, 107, 47–69.Google Scholar
  2. Burns, R.G. and Burns, V.M. (1977) Manganese oxides. Pp. 185–248 in: Marine Manganese Nodules (G.P. Glasby, editor). Elsevier, Amsterdam, The Netherlands.Google Scholar
  3. Chao, T.T. (1972) Selective dissolution of manganese oxides from soils and sediments with acidified hydroxylamine hydrochloride. Soil Science Society of America Proceedings, 36, 764–768.Google Scholar
  4. Davey, B.G. (1978) Soil structure as revealed by scanning electron microscopy. Pp. 97–102 in: Modification of Soil Structures (W.W. Emerson, editor). John Wiley & Sons, New York.Google Scholar
  5. Dixon, J.B. (1999) Instruction in HRTEM through the useful example of goethite in soils. Proceedings of the 11th International Clay Conference, Ottawa, Canada, pp. 385–808.Google Scholar
  6. Dixon, J.B. (2002) Soil Mineralogy: Recent Discoveries and their Implications. Report of the Department of Soil and Crop Sciences, Texas A & M University, College Station, Texas, USA, pp. 1–4.Google Scholar
  7. Eswaran, H., Stooops, G. and Sys, C. (1977) The micro-morphology of gibbsite forms in soils. Journal of Soil Science, 28, 136–143.Google Scholar
  8. Fendorf, S.E. and Zasoski, R.J. (1992) Chromium (III) oxidation by α-MnO2. 1. Characterization. Environmental Science Technology, 26, 79–85.Google Scholar
  9. Ford, R.G., Bertsch, P.M. and Seaman, J.C. (1997) Goethite morphologies investigated via X-ray diffraction of oriented samples. Clays and Clay Minerals, 45, 769–772.Google Scholar
  10. Golden, D.C., Chen, C.C., Dixon, J.B. and Tokashiki, Y. (1988) Pseudomorphic replacement of manganese oxides by iron oxide minerals. Geoderma, 42, 199–211.Google Scholar
  11. Golden, D.C., Dixon, J.B. and Kanehiro, Y. (1993) The manganese oxide minerals, lithiophorite in an Oxisol from Hawaii. Australian Journal of Soil Research, 31, 51–66.Google Scholar
  12. Grim, R.E., Bray, R.H. and Bradley, W.F. (1937) The mica in argillaceous sediments. American Mineralogist, 22, 813–829.Google Scholar
  13. Hsu, H.P. (1989) Aluminium hydroxides and oxyhydroxides. Pp. 331–378 in: Minerals in Soil Environments (J.B. Dixon and S.B. Weed, editors). Soil Science Society of America, Madison, Wisconsin.Google Scholar
  14. Islam, M.R., Stuart, R., Risto, A. and Vesa, P. (2002) Mineralogical changes during intense chemical weathering of sedimentary rocks in Bangladesh. Journal of Asian Earth Sciences, 20, 889–901.Google Scholar
  15. Jackson, M.L. (1969) Soil Chemical Analysis — Advanced Course, 2nd edition. Published by the author, University of Wisconsin, Madison, Wisconsin.Google Scholar
  16. Jeong, G.Y. (1998) Vermicular kaolinite epitactic on primary phyllosilicates in the weathering profiles of anorthosite. Clays and Clay Minerals, 46, 509–520.Google Scholar
  17. Lonsdale, P., Burns, V.M. and Fisk, M. (1980) Nodules of hydrothermal birnessite in the caldera of a young seamount. Journal of Geology, 88, 611–618.Google Scholar
  18. McDaniel, P.A. and Buol, S.W. (1991) Manganese distributions in acid soils of the North Carolina Piedmont. Soil Science Society of America Journal, 55, 152–158.Google Scholar
  19. McKenzie, R.M. (1989) Manganese oxides and hydroxides. Pp. 439–461 in: Minerals and Soil Environment (J.B. Dixon and S.B. Weed, editors). Soil Science Society of America, Madison, Wisconsin.Google Scholar
  20. Mehra, O.P. and Jackson, M.L. (1960) Iron oxide removal from soils and clays by dithionite citrate system buffered with sodium bicarbonate. Clays and Clay Minerals, 7, 317–327.Google Scholar
  21. Min Zhang, M. and Karathanasis, A.D. (1997) Characterization of iron-manganese concretions in Kentucky Alfisols with perched water table. Clays and Clay Minerals, 45, 428–439.Google Scholar
  22. Pauling, L. and Barclay, K. (1982) The crystal structure of lithiophorite. American Mineralogist, 67, 817.Google Scholar
  23. Peskleway, C.D., Henderson, G.S. and Wicks, F.J. (2003) Dissolution of gibbsite: Direct observation using fluid cell atomic force microscopy. American Mineralogist, 88, 8–26.Google Scholar
  24. Phillips, D.H., Ammons, J.T., Lee, S.Y. and Lietzke, D.A. (1998) Deep weathering of calcareous sedimentary rock and the redistribution of iron and manganese in soil and saprolite. Soil Science, 163, 71–81.Google Scholar
  25. Post, J.E. (1999) Manganese oxide minerals: crystal structures and eonomic and environmental significance. Proceedings of National Academy of Science of the United States of America, 96, 3447–3454.Google Scholar
  26. Post, J.E. and Appleman, D.E. (1994) Crystal-structure refinement of lithiophorite. American Mineralogist, 79, 370–374.Google Scholar
  27. Psyrillos, A., Howe, J.H., Manning, D.A.C. and Burley, S.D. (1999) Geological controls on kaolin particle shape and consequences for mineral processing. Clay Minerals, 34, 193–208.Google Scholar
  28. Ross, S.J., Franzmeier, D.P. and Roth, C.B. (1976) Mineralogy and chemistry of manganese oxides in some Indiana soils. Soil Science Society of America Journal, 40, 137–143.Google Scholar
  29. Schwertmann, U. and Kampf, N. (1988) Properties of goethite and hematite in kaolinitic soils of southern and central Brazil. Soil Science, 139, 344–350.Google Scholar
  30. Schwertmann, U. and Taylor, R.M. (1989) Iron Oxides. Pp. 379–438 in: Minerals in Soil Environments (J.B. Dixon and S.B. Weed, editors). Soil Science Society of America, Madison, Wisconsin.Google Scholar
  31. Sean, F., Andrew, R., Mei-Yin, L., Julian, G. and Gordon, P. (2000) Atomic modeling of gibbsite: surface structure and morphology. Journal of Crystal Growth, 209, 159–166.Google Scholar
  32. Sweegers, C., van Enckeort, W.J.P., Meekes, H., Bennema, P., Hiralal, I.D.K and Rijkeboer, A. (1999) The impact of twinning on the morphology of α-Al(OH)3 crystals. Journal of Crystal Growth, 197, 244–253.Google Scholar
  33. Tokashiki, Y., Dixon, J.B. and Golden, D.C. (1986) Manganese oxide analysis in soils by combined X-ray diffraction and selective dissolution methods. Soil Science Society of America Journal, 50, 1079–1083.Google Scholar
  34. Tokashiki, Y., Kai, N., Hentona, T., Shimo, M. and Vidhana Arachchi, L.P. (2003) A successive selective dissolution procedure for separation of birnessite, lithiophorite and goethite in manganese nodules. Soil Science Society of America Journal, 67, 837–843.Google Scholar
  35. Usui, A. and Mita, N. (1995) Geochemistry and morphology of a modern buserite concretion from a hot spring in Hokkaido, Japan. Clays and Clay Minerals, 43, 116–127.Google Scholar
  36. Uzochukwu, G.A. and Dixon, J.B. (1986) Manganese oxide minerals in nodules of two soils of Texas and Alabama. Soil Science Society of America Journal, 50, 1358–1363.Google Scholar
  37. White, N.G. and Dixon, J.B. (1986) Iron manganese distribution in nodules from a young Texas vertisol. Soil Science Society of America Journal, 60, 1254–1262.Google Scholar
  38. Yang, D.S. and Wang, M.K. (2003) Characterization and a fast method for synthesis of sub-micron lithiophorite. Clays and Clay Minerals, 51, 96–101.Google Scholar
  39. Zbiku, M. and Smart, R.St.C. (1998) Nanomorphology of kaolinites: comparative SEM and TEM studies. Clays and Clay Minerals, 46, 153–160.Google Scholar

Copyright information

© The Clay Minerals Society 2004

Authors and Affiliations

  • L. P. Vidhana Arachchi
    • 1
  • Y. Tokashiki
    • 2
    Email author
  • S. Baba
    • 2
  1. 1.Coconut Research InstituteLunuwilaSri Lanka
  2. 2.Department of Environmental Science and Technology, Faculty of AgricultureUniversity of the RyukyusNishihara-cho, OkinawaJapan

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