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Crystal structures of synthetic 7 Å and 10 Å manganates substituted by mono- and divalent cations

Published online by Cambridge University Press:  05 July 2018

Kenshi Kuma ,
Akira Usui ,
William Paplawsky ,
Benjamin Gedulin  and
Gustaf Arrhenius
Kenshi Kuma
Affiliation:
Department of Chemistry, Faculty of Fisheries, Hokkaido University, 3-1-1 Minato-cho, Hakodate, Hokkaido 041, Japan
Akira Usui
Affiliation:
Marine Geology Department, Geological Survey of Japan, 1-1-3 Higashi, Tsukuba, Ibaraki 305, Japan
William Paplawsky
Affiliation:
Scripps Institution of Oceanography, University of California at San Diego, La Jolla, CA 92093, USA
Benjamin Gedulin
Affiliation:
Scripps Institution of Oceanography, University of California at San Diego, La Jolla, CA 92093, USA
Gustaf Arrhenius
Affiliation:
Scripps Institution of Oceanography, University of California at San Diego, La Jolla, CA 92093, USA
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Abstract

The crystal structures of synthetic 7 Å and 10 Å manganates, synthetic birnessite and buserite, substituted by mono- and divalent cations were investigated by X-ray and electron diffractions. The monoclinic unit cell parameters of the subcell of lithium 7 Å manganate, which is one of the best ordered manganates, were obtained by computing the X-ray powder diffraction data: a = 5.152 Å, b = 2.845 Å, c = 7.196 Å, β = 103.08°. On the basis of the indices obtained by computing the X-ray diffraction data of Li 7 Å manganate, monovalent Na, K and Cs and divalent Be, Sr and Ba 7 Å manganates were interpreted as the same monoclinic structure with β = 100–103° as that of Li 7 Å manganate, from their X-ray diffraction data. In addition, divalent Mg, Ca and Ni 10 Å manganates were also interpreted as the same monoclinic crystal system with β = 90–94° The unit cell parameters, especially a, c and β, change possibly with the type of substituent cation probably because of the different ionic radius, hydration energy and molar ratio of substituent cation to manganese. However, these diffraction data, except for those of Sr and Ba 7 Å and Ca and Ni 10 Å manganates, reveal only some parts of the host manganese structure with the edge-shared [MnO6] octahedral layer. On the other hand, one of the superlattice reflections observed in the electron diffractions was found in the X-ray diffraction lines for heavier divalent cations Sr and Ba 7 Å and Ca and Ni 10 Å manganates. The reflection presumably results from the substituent cation position in the interlayer which is associated with the vacancies in the edge-shared [MnO6] layer and indicates that the essential vacancies are linearly arranged parallel to the b-axis. Furthermore, the characteristic superlattice reflection patterns for several cations, Li, Mg, Ca, Sr, Ba and Ni, manganates were interpreted that the substituent cations are regularly distributed in the interlayer according to the exchange percentage of substituent cation to Na+. In contrast, the streaking in the a-direction observed strongly in the electron diffractions for heavier monovalent cations, K and Cs, manganates probably results from the disordering of their cations in the a-direction in the interlayer.

Keywords

7 Å manganate10 Å manganateX-ray diffractionelectron diffractioncrystal structure
Type
Mineralogy
Information
Mineralogical Magazine , Volume 58 , Issue 392 , September 1994 , pp. 425 - 447
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 1994

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References

Ahrens, L. H. (1952) The use of ionization potentials. Part 1. ionic radii of the elements. Geochim. Cosmochim. Acta, 2, 155–69.Google Scholar
Arrhenius, G. and Tsai, A. G. (1981) Structure, phase transformation and prebiotic catalysis in marine manganate minerals. Scripps Inst. Oceanogr. Ref. Ser., 81, 1–19.Google Scholar
Arrhenius, G., Cheung, K. Crane, S., Fisk, M., Frazer, J., Korkisch, J., Mellin, T., Nakao, S., Tsai, A., and Wolf, G. (1979) Counterions in marine manganates. In La Genise des Nodules de Manganese, (Lalou, C., ed.), Colloq. Int. C. N. R. S., 289, 333–56.Google Scholar
Beeston, B. E. P., Home, R. W. and Markham, R. (1972) Electron diffraction and optical diffraction techniques. In Practical Methods in Electron Microscopy, (A. M. Glauert, ed.), Vol. 1, Part II, North-Holland/Elsevier, New York, 444 pp.Google Scholar
Burns, R. G. and Burns, V. M. (1977) The mineralogy and crystal chemistry of deep-sea manganese nodules, a polymetallic resource of the twenty-first century. Phil. Trans. R. Soc. Lond. A., 286, 283–301.Google Scholar
Burns, R. G. and Burns, V. M. (1979) Manganese oxides. In Marine Minerals, (R. G. Burns, ed.), Short Course Notes, Vol. 6, Miner. Soc. Amer., Washington, D. C, pp. 1-46.Google Scholar
Burns, R. G. and Burns, V. M. (1981) Authigenic oxides. In The Sea, VoL 7: The Oceanic Litho-sphere, (C. Emiliani, ed.), John Wiley, New York, pp. 875-914.Google Scholar
Burns, V. M. and Burns, R. G. (1978) Post-depositional metal enrichment processes inside manganese nodules from the north equatorial Pacific. Earth Planet. Sci. Lett., 39, 341–8.Google Scholar
Buser, W. and Graf, P. (1955a) Radiochemische Untersuchungen an Festkorpern, III. Ionen-und Isotopenaustauschreaktionen an Mangandioxy-den und Manganiten. Helv. Chim. Acta, 38, 810–29.Google Scholar
Buser, W. and Graf, P. (19556) Differenzierung von Mangan (II) manganit und S-MnO2 durch Oberflachenmessung nach Brunauer-Emmett-Teller. Helv. Chim. Acta, 38, 830–4.Google Scholar
Buser, W. and Griitter, A. (1956) Uber die Nature der Manganknollen. Schweiz Mineral Petrogr. Mitt., 36, 49–62.Google Scholar
Chukhrov, F. V., Gorshkov, A. I., Rudnitskaya, E. S. and Sivtsov, A. V. (1978) The characteristics of birnessite. Izvest. Akad. Nauk SSSR, ser. geol., no. 9, 67–76.Google Scholar
Chukhrov, F. V., Gorshkov, A. I., Sivtsov, A. V. and Berezovskaya, V. V. (1979a) A new 14 A mineral of the birnessite group in deep-sea micronodules. Nature, 280, 136–7.Google Scholar
Chukhrov, F. V., Gorshkov, A. I., Sivtsov, A. V. and Berezovskaya, V. V. (19796) New mineral phases of oceanic manganese microconcretions. Izvest. Akad. Nauk SSSR,, ser. geol., no. 1, 83–90.Google Scholar
Chukhrov, F. V., Gorshkov, A. I., Vitovskaya, I. V., Drits, V. A., Sivtsov, A. I. and Rudnitskaya, Ye. S. (1980) Crystallochemical nature of Co-Ni asbolan. AN SSSR Izvestiya, ser. geol., no. 6, 73–81.Google Scholar
Chukhrov, F. V., Gorshkov, A. I., Vitovskaya, I. V., Drits, V. A., Sivtsov, A. I. and Rudnitskaya, Ye. S. (Trans. Intemat. Geol. Rev., 24, 598-604.Google Scholar
Corliss, J. B., Lyle, M., Dymond, J. and Crane, K. (1978) The chemistry of hydrothermal mounds near the Galapagos rift. Earth Planet. Sci. Lett., 40, 12–24.Google Scholar
Crane, S. E. (1981) Structural chemistry of the marine manganate minerals. Ph.D. thesis (unpubl.), University of California, San Diego, 296 pp.Google Scholar
Cronan, D. S., Glasby, G. P., Moorby, S. A., Thomson, J., Knedler, K. E. and McDougall, J. C. (1982) A submarine hydrothermal manganese deposit from the south-west Pacific island arc. Nature, 298, 456–8.Google Scholar
Cullity, B. D. (1978) Elements of X-ray diffraction, 2nd ed., Addison-Wesley, 555 pp.Google Scholar
Feitknecht, W. and Marti, W. (1945) Uber die Oxydation von Mangan(Il) hydroxid mit moleku-larem Sauerstoff. Heh. Chim. Ada, 28, 129–56.Google Scholar
Giovanoli, R. (1980) On natural and synthetic manganese nodules. In Geology and Geochemistry of Manganese, (I. M. Varentsov and Gy. Grass-elly, eds.), Akad. Kiado, Budapest, Vol. 1, pp. 159-202.Google Scholar
Giovanoli, R. and Briitsch, R. (1979) Uber die Oxidhydroxide des Mn(IV) mit Schichtengitter. 5 Mitteilung: Stochiometrie, Austauschverhalten und die Rolle bei der Bindung von Tiesee-Mangankonkretionen. Chimia, 33, 372–6.Google Scholar
Giovanoli, R. and Biirki, P. (1975) Comparison of x-ray evidence of marine manganese nodules and non-marine manganese ore deposits. Chimia, 29, 266–9.Google Scholar
Giovanoli, R., Stahli, E. and Feitknecht, W. (1970a) Uber Oxidhydroxide des vierwertigen Mangans mit Schichtengitter. 1. Natrium-mangan 11,111) manganat (IV). Heh. Chim. Ada, 53, 209–20.Google Scholar
Giovanoli, R., Stahli, E. and Feitknecht, W. (19706) Uber Oxihydroxide des vierwertigen Mangans mit Schichtengitter. 2. Mangan (II)-Manganat (IV). Heh. Chim. Acta, 53, 453–64.Google Scholar
Giovanoli, R., Biihler, H. and Sokolowska, K. (1973) Synthetic lithiophorite: electron microscopy and x-ray diffraction. J. Microsc, 18, 271–84.Google Scholar
Giovanoli, R., Biirki, P., Giuffredi, S. and Stumm, W. (1975) Layer structured manganese oxide hydroxides. IV: The buserite group; structure stabilization of transition elements. Chimia, 29, 517–20.Google Scholar
Glasby, G. P. (1972) The mineralogy of manganese nodules from a range of marine environments. Mar. Geol, 13, 57–72.Google Scholar
Hariya, Y. (1980) On the geochemistry and formation of manganese dioxide deposits. In Geology and Geochemistry of Manganese (I. M. Varentsov and Gy. Grasselly, eds.), Akad. Kiado, Budapest, Vol. 1, pp. 353-66.Google Scholar
Manceau, A., Llorca, S. and Calas, G. (1987) Crystal chemistry of cobalt and nickel in lithiophorite and asbolane from New Caledonia. Geochim. Cosmo-chim. Acta, 51, 105–13.Google Scholar
McKenzie, R. M. (1971) The synthesis of birnessite, cryptomelane, and some other oxides and hydro-xides of manganese. Mineral. Mag., 28, 493–503.Google Scholar
Mellin, T. (1981) Structural chemistry of synthetic manganate and iron compounds: implication for geochemistry of marine ferromanganese deposits. Ph.D. thesis (unpubl.), University of Goteborg, Goteborg, 237 pp.Google Scholar
Moore, W. S. and Vogt, P. R. (1976) Hydrothermal manganese crusts from two sites near the Galapagos spreading axis. Earth Planet. Sci. Lett., 29, 349–56.Google Scholar
Post, J. E. and Veblen, D. R. (1990) Crystal structure determinations of synthetic sodium, magnesium, and potassium birnessite using TEM and the Rietveld method. Amer. Mineral, 75, 477–89.Google Scholar
Potter, R. M. and Rossman, G. R. (1979) The tetravalent manganese oxides: identification, hy-dration, and structural relationships by infrared spectroscopy. Amer. Mineral, 64, 1199–218.Google Scholar
Rosseinsky, D. R. (1965) Electrode potentials and hydration theories and correlations. Chem. Rev., 65, 467–90.Google Scholar
Shannon, R. D. and Prewitt, C. T. (1969) Effective ionic radii in oxides and fluorides. Acta. Crystal-logr., B25, 925–46.Google Scholar
Stouff, P. and Boulegue, J. (1988) Synthetic 10-A and 7-A phyllomanganates: their structures as determined by EXAFS. Amer. Mineral, 73, 1162–9.Google Scholar
Stouff, P. and Boulegue, J. (1989) Geochemistry and crystallochemistry of oceanic hydrothermal man-ganese oxyhydroxides showing Mn-Cu associa-tion. Geochim. Cosmochim. Acta, 53, 833–43.Google Scholar
Tejedor-Tejedor, M. I. and Paterson, E. (1978) Reversibility of lattice collapse in synthetic buserite. Int. Clay Conf, 27, 501–8.Google Scholar
Turner, S., Siegel, M. D. and Buseck, P. R. (1982) Structural features of todorokite intergrowths in manganese nodules. Nature, 296, 841–3.Google Scholar
Usui, A. (1979) Mineralogical study of marine manganese nodules, synthesis of hydrous manga-nese oxides, and their implication to the genesis and geochemistry. Ph.D. thesis (unpubl.), University of Tokyo, Tokyo, 175 pp.Google Scholar
Usui, A. and Nishimura, A. (1992) Submersible observations of hydrothermal manganese deposits on the Kaikata seamount, Izu-Ogasawara (Bonin) arc. Mar. Geol., 106, 203–16.Google Scholar
Usui, A., Takenouchi, S. and Shoji, T. (1978) Mineralogy of deep sea manganese nodules and synthesis of manganese oxides: implication to genesis and geochemistry. Mining Geol., 28, 405–20. (In Japanese with English abstr.).Google Scholar
Usui, A., Melline, T. A., Nohara, M. and Yuasa, M. (1989) Structural stability of marine 10 A manganates from the Ogasawara (Bonin) Arc: Implication for low-temperature hydrothermal activity. Mar. Geol., 86, 41–56.Google Scholar
Visser, J. W. (1969) A fully automatic program for finding the unit cell from powder data. Appl. Cryst., 2, 89–95.Google Scholar
Wadsley, A. D. (1950a) A hydrous manganese oxide with exchange properties. J. Amer. Chem. Soc., 72, 1782–4.Google Scholar
Wadsley, A. D. (1950b) Synthesis of some hydrated manganese minerals. Amer. Mineral., 35, 485–99.Google Scholar
Wadsley, A. D. (1952) The structure of lithiophorite, (Al,Li)MnO2(OH)2 . Ada Crystallogr., 5, 676–80.Google Scholar
Wadsley, A. D. (1955) The crystal structure of chalcophanite, ZnMn3O7.3H2O. Ada Crystallogr., 8, 165–72.Google Scholar