Mineralogy and Petrology

, Volume 112, Issue 2, pp 173–184 | Cite as

Crystal chemistry and oxidation state of Fe-rich prehnite from a hydrothermally altered dolerite

  • Mariko Nagashima
  • Kiyoka Iwasa
  • Masahide Akasaka
Original Paper


Fe-rich prehnite, Ca2(Al,Fe)(AlSi3)O10(OH)2, in a hydrothermally altered dolerite sill from Mitsu, Shimane Peninsula, Japan, was studied using 57Fe Mössbauer spectroscopy and X-ray Rietveld method to determine the oxidation state and distribution of Fe within the prehnite and to clarify its structural properties. Prehnite shows two modes of occurrence: a druse and vein mineral (prehnite I) associated with Fe-rich pumpellyite and laumontite and a replacement of primary plagioclase (prehnite II). The Fe contents of prehnite I and II are 0.33–0.44 and 0.01–0.46 Fe3+ atoms per formula unit, respectively. The Mössbauer spectrum of prehnite II consists of one doublet with isomer shift (IS) = 0.364 mm/s and quadrupole splitting (QS) = 0.284 mm/s assigned to Fe3+ at the octahedral M site. In contrast, the Mössbauer spectrum of prehnite I consists of two doublets assigned to Fe3+ at the M site (IS = 0.369 mm/s and QS = 0.299 mm/s) and Fe2+ at the seven coordinated A site (IS = 1.05 and QS = 2.78 mm/s). According to X-ray Rietveld refinements with Pmna and Pma2 space groups, the fitting with Pma2 gave more reduced reliability factors than those using Pmna for both specimens, implying ordering of Al and Si at the tetrahedral T2 sites. Determined T2–O bond lengths at the Al-rich and Si-rich T2 sites, 1.71–1.72 and 1.62–1.64 Å, respectively, also indicate the ordered arrangement of Al and Si at the T2 sites. Refined site occupancies at the A and M sites are represented as A (Ca0.993(9)Fe2 +0.007) M (Al0.666(6)Fe3 +0.334) for prehnite I, and A Ca1.0 M (Al0.865(5)Fe3 +0.135) for prehnite II, respectively. The existence of Fe2+ in the A site filling Ca deficiency in prehnite I is consistent with the result from the Mössbauer analysis.


Prehnite Fe Mössbauer spectroscopy Rietveld method 



We thank Dr. Barry Roser for his critical reading of manuscript, Dr. M. Broekmans Editor-in-Chief, and two anonymous reviewers for their constructive comments.


  1. Akasaka M, Shinno I (1992) Mössbauer spectroscopy and its recent application to silicate mineralogy. J Miner Soc Jpn 21:3–20 (Japanese with English abstract)Google Scholar
  2. Akasaka M, Kimura Y, Omori Y, Sakakibara M, Shinno I, Togari K (1997) 57Fe Mössbauer study of pumpellyite-okhotskite-julgoldite series minerals. Miner Petrol 61: 181–198CrossRefGoogle Scholar
  3. Akasaka M, Hashimoto H, Makino K, Hino R (2003) 57Fe Mössbauer and X-ray Rietveld studies of ferrian prehnite from Kouragahana, Shimane Peninsula, Japan. J Miner Petrol Sci 98:31–40CrossRefGoogle Scholar
  4. Akizuki M (1987) Al, Si order and the internal texture of prehnite. Can Miner 25: 707–716Google Scholar
  5. Artioli G, Quartieri S, Deriu A (1995) Spectroscopic data on coexisting prehnite-pumpellyite and epidote-pumpellyite. Can Miner 33: 67–75CrossRefGoogle Scholar
  6. Balić-Žunić T, Šćavničar S, Molin G (1990) Crystal structure of prehnite from Komiža. Eur J Miner 2: 731–734CrossRefGoogle Scholar
  7. Baur WH, Joswig W, Kassner D, Hofmeister W (1990) Prehnite: structural similarity of the monoclinic and orthorhombic polymorphs and their Si/Al ordering. J Solid State Chem 86:330–333CrossRefGoogle Scholar
  8. Bertaut EF (2006) Symbols for space groups. In: Hahn T (ed) International tables for crystallography, Vol. A, 5th ed. Chap. 4.3. International Union of Crystallography. Springer Verlag, The Netherlands, pp. 62–76Google Scholar
  9. Deer WA, Howie RA, Zussman J (2013) An introduction to the rock-forming minerals. 3rd ed. The Mineralogical Society, London. 549pGoogle Scholar
  10. Detrie TA, Ross NL, Angel RJ, Welch MD (2008) Crystal chemistry and location of hydrogen atoms in prehnite. Mineral Mag 72: 1163–1179CrossRefGoogle Scholar
  11. Detrie TA, Ross NL, Angel RJ, Gatta GD (2009) Equation of state and structure of prehnite to 9.8GPa. Eur J Mineral 21: 561–570CrossRefGoogle Scholar
  12. Dollase WA (1986) Correction of intensities for preferred orientation in powder diffractometry: application of the March model. J Appl Crystallogr 19:267–272CrossRefGoogle Scholar
  13. Hill RJ, Flack HD (1987) The use of the Durbin–Watson d statistic in Rietveld analysis. J Appl Crystallogr 20:356–361CrossRefGoogle Scholar
  14. Izumi F (1993) Rietveld analysis program RIETAN and PREMOS and special applications. In: Young RA (ed) The Rietveld method. Oxford Science Publications, Oxford, pp 236–253Google Scholar
  15. Izumi F, Momma K (2007) Three-dimensional visualization in powder diffraction. Sol St Phen 130: 15–20CrossRefGoogle Scholar
  16. Jones JB (1967) Al-O and Si-O tetrahedral distance in aluminosilicate framework structures. Acta Crystallogr B 24:355–358CrossRefGoogle Scholar
  17. Kano K, Yoshida F (1985) Geology of the Sakaiminato district. Quadrangle Series, scale 1:50,000, Geological Survey of Japan, 57p. (in Japanese)Google Scholar
  18. Kano K, Satoh H, Bunno M (1986) Iron-rich pumpellyite and prehnite from the Miocene gabbroic sills of the Shimane Peninsula, Southwest Japan. J Jpn Assoc Mineral Petrol Econ Geol 81:51–56CrossRefGoogle Scholar
  19. Levien L, Prewitt CT, Weidner DJ (1980) Structure and elastic properties of quartz at pressure. Am Miner 65: 920–930Google Scholar
  20. Michailidis K, Kassoli-Fournaraki A, Ericsson T, Eilippidis A, Godelitsas A (1995) Prehnite formation and metamorphic relations in the metagabbros of Oreokastro ophiolite suite, Macedonia, Greece. GFF 117: 15–21CrossRefGoogle Scholar
  21. Momma K, Izumi F (2011) VESTA3 for three-dimensional visualization of crystal, volumetric and morphology data. J Appl Crystallogr 44:1257–1276CrossRefGoogle Scholar
  22. Nagashima M, Iwasa K, Akasaka M (2016) Relation between occurrence and chemical compositions of prehnite in hydrothermally altered dolerite from Mitsu, Shimane Peninsula, Japan. Geosci Rep Shimane Univ 34: 1–8 (in Japanese with English abstract)Google Scholar
  23. Organization Committee of Geological Map of Shimane Prefecture (1997) Geological map of Shimane Prefecture, scale 1:200,000. Department of Geoscience, Shimane UniversityGoogle Scholar
  24. Papike JJ, Zoltai T (1967) Ordering of tetrahedral aluminum in prehnite. Ca2(Al,Fe+3)[Si3AlO10](OH)2. Am Mineral 52: 974–984Google Scholar
  25. Peng S-T, Chou K-D, Tang Y-C (1959) The structure of prehnite. Acta Chim Sin 25: 56–63 (in Chinese)Google Scholar
  26. Preisinger A (1965) Prehnit-ein neuer Schichtsilikattyp. Tschermaks Mineral Petrogr Mitt 10: 491–504 (in German)CrossRefGoogle Scholar
  27. Reddy NCG, Fayazyddin S Md, Reddy RRS, Reddy GS, Reddy SL, Rao PS, Reddy BJ (2005) Characterisation of prehnite by EPMA, Mössbauer, optical absorption and EPR spectroscopic methods. Spectrochim Acta A 62:71–75CrossRefGoogle Scholar
  28. Robinson K, Gibbs GV, Ribbe PH (1971) Quadratic elongation: a quantitative measure of distortion in coordination polyhedra. Science 172:567–570CrossRefGoogle Scholar
  29. Young RA (1993) Introduction to the Rietveld method. In: Young RA (ed) The Rietveld method. Oxford Science Publications, Oxford, pp 1–38Google Scholar

Copyright information

© Springer-Verlag GmbH Austria 2017

Authors and Affiliations

  1. 1.Division of Earth Science, Graduate School of Science and Technology for InnovationYamaguchi UniversityYamaguchiJapan
  2. 2.Department of Geosphere Science, Faculty of ScienceYamaguchi UniversityYamaguchiJapan
  3. 3.Department of Geoscience, Interdisciplinary Graduate School of Science and EngineeringShimane UniversityMatsueJapan

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