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Water molecules in beryl and cordierite: high-temperature vibrational behavior, dehydration, and coordination to cations

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Abstract

Natural samples of typical cyclosilicates beryl and cordierite include water and carbon dioxide molecules in channels formed by the open cavities. Water molecules in the channels have two forms that are distinguished by whether they coordinate to extra-framework cations (type II) or not (type I). We measured polarized infrared (IR) spectra for thin sections of the (100) plane of beryl or the (100) and (010) planes (cb and ca planes) of cordierite under various temperature conditions. The spectral features of major bands clearly showed the distinguishable behavior of types I and II water molecules under high temperature as follows. Over the temperature range from room temperature to 800°C where rapid dehydration did not occur, the decrease in band heights for type II water molecules were smaller than those for type I, and band shifts were more predominant for type II water molecules. The decrease in band heights and band shifts of type I/II bands differed also for beryl and cordierite, which arises from the different ways in which water molecules are fixed in the channels. Dehydration was enhanced at 850°C. The IR spectra at room temperature quenched from 850°C both for beryl and cordierite showed that the vibrational bands related to type II water molecules were stable after those related to type I water molecules disappeared. In addition, frequency changes of type II bands were observed, possibly because of changes of coordination states of type II water molecules to extra-framework cations in the channels.

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References

  • Adamo I, Gatta GD, Rotiroti N, Diella V, Pavese A (2008) Gemmological investigation of a synthetic blue beryl: a multi-methodological study. Mineral Mag 72:799–808

    Article  Google Scholar 

  • Aines RD, Rossman GR (1984) The high temperature behavior of water and carbon dioxide in cordierite and beryl. Am Mineral 69:319–327

    Google Scholar 

  • Andersson LO (2006) The positions of H+, Li+ and Na+ impurities in beryl. Phys Chem Minerals 33:403–416

    Article  Google Scholar 

  • Artioli G, Rinaldi R, Ståhl K, Zanazzi PF (1993) Structure refinements of beryl by single-crystal neutron and X-ray diffraction. Am Mineral 78:762–768

    Google Scholar 

  • Artioli G, Rinaldi R, Wilson CC, Zanazzi PF (1995) Single-crystal pulsed neutron diffraction of a highly hydrous beryl. Acta Crystallogr B51:733–737

    Google Scholar 

  • Aurisicchio C, Fioravanti G, Grubessi O, Zanazzi PF (1988) Reappraisal of the crystal chemistry of beryl. Am Mineral 73:826–837

    Google Scholar 

  • Aurisicchio C, Grubessi O, Zecchini P (1994) Infrared spectroscopy and crystal chemistry of the beryl group. Can Mineral 32:55–68

    Google Scholar 

  • Balan E, Delattre S, Guillaumet M, Salje EKH (2010) Low-temperature infrared spectroscopic study of OH-stretching modes in kaolinite and dickite. Am Mineral 95:1257–1266

    Article  Google Scholar 

  • Bauschlicher CW, Langhoff SR, Partridge H, Rice JE, Komornicki A (1991) A theoretical study of Na(H2O) + n (n = 1–4). J Chem Phys 95:5142–5148

    Article  Google Scholar 

  • Carey JW, Navrotsky A (1992) The molar enthalpy of dehydration of cordierite. Am Mineral 77:930–936

    Google Scholar 

  • Charoy B, de Donato P, Barres O, Pinto-Coelho C (1996) Channel occupancy in an alkali-poor beryl from Serra Branca (Goias, Brazil): spectroscopic characterization. Am Mineral 81:395–403

    Google Scholar 

  • Deer WA, Howie RA, Zussman J (1992) An introduction to the rock-forming minerals, 2nd edn. Longman, London, pp 122–129

    Google Scholar 

  • Della Ventura G, Bellatreccia F, Cesare B, Harley S, Piccinini M (2009) FTIR microspectroscopy and SIMS study of water-poor cordierite from El Hoyazo, Spain: application to mineral and melt devolatilization. Lithos 113:498–506

    Article  Google Scholar 

  • Fukuda J, Shinoda K (2008) Coordination of water molecules with Na+ cations in a beryl channel as determined by polarized IR spectroscopy. Phys Chem Minerals 35:347–357

    Article  Google Scholar 

  • Fukuda J, Shinoda K, Nakashima S, Miyoshi N, Aikawa N (2009a) Polarized infrared spectroscopic study of diffusion of water molecules along channels of beryl structure. Am Mineral 91:981–985

    Article  Google Scholar 

  • Fukuda J, Yokoyama T, Kirino Y (2009b) Characterization of the states and diffusivity of intergranular water in a chalcedonic quartz by high-temperature in situ infrared spectroscopy. Mineral Mag 73:825–835

    Article  Google Scholar 

  • Gatta GD, Nestola F, Nestola F, Bromiley GD, Mattauch S (2006) The real topological configuration of the extra-framework content in alkali-poor beryl: a multi-methodological study. Am Mineral 91:29–34

    Article  Google Scholar 

  • Geiger CA, Kolesov BA (2002) Microscopic-macroscopic relationships in silicates: examples from IR and Raman spectroscopy and heat capacity measurements. In: Gramaccioli CM (ed) Energy Modeling in Minerals. European Notes in Mineralogy 4. Eötrös University Press, Budapest, pp 347–387

  • Gibbs GV (1966) The polymorphism of cordierite I: the crystal structure of low cordierite. Am Mineral 51:1068–1087

    Google Scholar 

  • Gibbs GV, Breck DW, Meagher EP (1968) Structural refinement of hydrous and anhydrous synthetic beryl, Al2(Be3Si6)O18 and emerald, Al1.9Cr0.1(Be3Si6)O18. Lithos 1:275–285

    Article  Google Scholar 

  • Goldman DS, Rossman GR, Dollase WA (1977) Channel constituents in cordierite. Am Mineral 62:1144–1157

    Google Scholar 

  • Grant K, Gleeson SA, Roberts S (2003) The high-temperature behavior of defect hydrogen species in quartz: implications for hydrogen isotope studies. Am Mineral 88:262–270

    Google Scholar 

  • Hawthorne FC, Černý P (1977) The alkali-metal positions in Cs–Li beryl. Can Mineral 15:414–421

    Google Scholar 

  • Herzberg G (1956) Infrared and Raman spectra of polyatomic molecules. D. Van Nostrand Company, New York

    Google Scholar 

  • Johannes W, Schreyer W (1981) Experimental introduction of CO2 and H2O into Mg-cordierite. Am J Sci 281:299–317

    Article  Google Scholar 

  • Kolesov BA (2008) Vibrational states of H2O in beryl: physical aspects. Phys Chem Minerals 35:271–278

    Article  Google Scholar 

  • Kolesov BA, Geiger CA (2000a) The orientation and vibrational states of H2O in synthetic alkali-free beryl. Phys Chem Minerals 27:557–564

    Article  Google Scholar 

  • Kolesov BA, Geiger CA (2000b) Cordierite II: the role of CO2 and H2O. Am Mineral 85:1265–1274

    Google Scholar 

  • Lee HM, Tarakeshwar P, Park J, Kolaski MR, Yoon YJ, Yi HB, Kim WY, Kim KS (2004) Insights into the structures, energetics, and vibrations of monovalent cation-(water)1–6 clusters. J Phys Chem A108:2949–2958

    Google Scholar 

  • Łodziński M, Sitarz M, Stec K, Kozanecki M, Fojud Z, Jurga S (2005) ICP, IR, Raman, NMR investigations of beryls from pegmatites of the Sudety Mts. J Mol Struct 744:1005–1015

    Article  Google Scholar 

  • Loewenstein W (1954) The distribution of aluminum in the tetrahedra of silicates and aluminates. Am Mineral 39:92–96

    Google Scholar 

  • Mathew G, Karanth RV, Gundu Rao TK, Deshpande RS (1997) Channel constituents of alkali-poor Orissan beryls: an FT-IR spectroscopic study. Curr Sci 73:1004–1011

    Google Scholar 

  • Nakamoto K, Margoshes M, Rundle RE (1955) Stretching frequencies as a function of distances in hydrogen bonds. J Am Chem Soc 77:6480–6486

    Article  Google Scholar 

  • Pankrath R, Langer K (2002) Molecular water in beryl, VIAl2[Be3Si6O18] · nH2O, as a function of pressure and temperature: an experimental study. Am Mineral 87:238–244

    Google Scholar 

  • Paukov IE, Kovalevskaya YA, Rahmoun NS, Geiger CA (2007) Heat capacity of synthetic hydrous Mg-cordierite at low temperatures: thermodynamic properties and the behavior of the H2O molecule in selected hydrous micro and nanoporous silicates. Am Mineral 92:388–396

    Article  Google Scholar 

  • Salje EKH, Wruck B, Thomas H (1991) Order-parameter saturation and low-temperature extension of Landau theory. Z Phys 82:399–404

    Article  Google Scholar 

  • Tokiwai K, Nakashima S (2010) Integral molar absorptivities of OH in muscovite at 20–650°C by in situ high-temperature IR microspectroscopy. Am Mineral 95:1052–1059

    Article  Google Scholar 

  • Tsurusawa T, Iwata S (1999) Theoretical studies of structures and ionization threshold energies of water cluster complexes with a group 1 metal, M(H2O) n (M = Li and Na). J Phys Chem A103:6134–6141

    Google Scholar 

  • Tsurusawa T, Iwata S (2000) Electron-hydrogen bonds and OH harmonic frequency shifts in water cluster complexes with a group 1 metal atom, M(H2O) n (M = Li and Na). J Chem Phys 112:5705–5710

    Article  Google Scholar 

  • Wilson EB, Decius JC, Cross PC (1955) Molecular vibrations: the theory of Infrared and Raman vibrational spectra. McGraw-Hill, New York

    Google Scholar 

  • Wood DL, Nassau K (1967) Infrared spectra of foreign molecules in beryl. J Chem Phys 47:2220–2228

    Article  Google Scholar 

  • Wood DL, Nassau K (1968) The characterization of beryl and emerald by visible and infrared absorption spectroscopy. Am Mineral 53:777–800

    Google Scholar 

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Acknowledgments

We thank H. Masuda and K. Okazaki for supporting analyses of AAS and ICP and for helpful comments regarding the results obtained. We also thank T. Okudaira for supporting the operation of WDS. We thank F. Bellatreccia, I. Adamo, and L. Andersson for very thorough reviews of an earlier draft, and M. Kurosawa and an anonymous reviewer for official reviews. Comments from the editor, M. Matsui greatly improved the manuscript. This work was financially supported by a Grant-in-Aid for Scientific Research (212327) awarded to J. Fukuda by the Japan Society for the Promotion of Science for Young Scientists.

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Authors and Affiliations

  1. Department of Earth and Space Science, Graduate School of Science, Osaka University, 1-1 Machikaneyama, Toyonaka, Osaka, 560-0043, Japan

    J. Fukuda

  2. Department of Geosciences, Graduate School of Science, Osaka City University, 3-3-138 Sugimoto, Sumiyoshi, Osaka, 558-8585, Japan

    K. Shinoda

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  1. J. Fukuda
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Correspondence to J. Fukuda.

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Fukuda, J., Shinoda, K. Water molecules in beryl and cordierite: high-temperature vibrational behavior, dehydration, and coordination to cations. Phys Chem Minerals 38, 469–481 (2011). https://doi.org/10.1007/s00269-011-0420-9

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