The crystal chemistry of pumpellyite from Sugashima and julgoldite from Kouragahana, Japan: Toward a comprehensive understanding of the crystal chemistry of pumpellyite-group minerals
Single-crystal X-ray crystal-structure refinements and electron-microprobe analyses of julgoldite from Kouragahana, Shimane Peninsula, and pumpellyite from Sugashima, Mie, Japan yielded the compositions of WCa2.00X(Fe0.69Mg0.20Al0.11)Σ1.00Y(Fe3+1.46Al0.54)Σ2.00Si3.00O14−n(OH)n and WCa2.00X(Al0.56Mg0...
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          | Published in | Journal of Mineralogical and Petrological Sciences Vol. 120; no. 1; p. 250401 | 
|---|---|
| Main Authors | , | 
| Format | Journal Article | 
| Language | English | 
| Published | 
        Sendai
          Japan Association of Mineralogical Sciences
    
        2025
     Japan Science and Technology Agency  | 
| Subjects | |
| Online Access | Get full text | 
| ISSN | 1345-6296 1349-3825 1349-3825  | 
| DOI | 10.2465/jmps.250401 | 
Cover
| Abstract | Single-crystal X-ray crystal-structure refinements and electron-microprobe analyses of julgoldite from Kouragahana, Shimane Peninsula, and pumpellyite from Sugashima, Mie, Japan yielded the compositions of WCa2.00X(Fe0.69Mg0.20Al0.11)Σ1.00Y(Fe3+1.46Al0.54)Σ2.00Si3.00O14−n(OH)n and WCa2.00X(Al0.56Mg0.35Fe0.09)Σ1.00YAl2.00Si3.00O14−n(OH)n (4 ≥ n ≥ 3), respectively. The latter was classified as pumpellyite-(Al), while the former can only be concluded to be either julgoldite-(Fe3+) or julgoldite-(Fe2+). The hydroxyl groups determined by structure refinement are consistent with those known for pumpellyite. The length of the b-axis most accurately reflects the average size of ionic radii at the Y site based on structural and chemical data for pumpellyite-group minerals. In contrast, the lengths of the a- and c-axes demonstrate a favorable correlation with the mean ionic radius of the Y site; however, they exhibit greater dispersion compared to the b-axis. This is attributed to the lateral expansion or shrinkage of the (010) plane caused by variation in the size of the X site. Therefore, the pumpellyite group minerals with longer a- and c-axes may be rich in divalent cations at the X site. The well-defined, intense Raman peak around 695 cm−1 is characteristic of pumpellyite-group minerals and is likely attributed to the Si-O-Si bending mode. The six to seven Raman peaks resulting from O-H bond stretching reflect the complex hydrogen bond system in the pumpellyite group structure, arising from the presence of multiple hydroxyl groups and variations in the local chemical environment due to compositional differences. | 
    
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| AbstractList | Single-crystal X-ray crystal-structure refinements and electron-microprobe analyses of julgoldite from Kouragahana, Shimane Peninsula, and pumpellyite from Sugashima, Mie, Japan yielded the compositions of WCa2.00X(Fe0.69Mg0.20Al0.11)Σ1.00Y(Fe3+1.46Al0.54)Σ2.00Si3.00O14−n(OH)n and WCa2.00X(Al0.56Mg0.35Fe0.09)Σ1.00YAl2.00Si3.00O14−n(OH)n (4 ≥ n ≥ 3), respectively. The latter was classified as pumpellyite-(Al), while the former can only be concluded to be either julgoldite-(Fe3+) or julgoldite-(Fe2+). The hydroxyl groups determined by structure refinement are consistent with those known for pumpellyite. The length of the b-axis most accurately reflects the average size of ionic radii at the Y site based on structural and chemical data for pumpellyite-group minerals. In contrast, the lengths of the a- and c-axes demonstrate a favorable correlation with the mean ionic radius of the Y site; however, they exhibit greater dispersion compared to the b-axis. This is attributed to the lateral expansion or shrinkage of the (010) plane caused by variation in the size of the X site. Therefore, the pumpellyite group minerals with longer a- and c-axes may be rich in divalent cations at the X site. The well-defined, intense Raman peak around 695 cm−1 is characteristic of pumpellyite-group minerals and is likely attributed to the Si-O-Si bending mode. The six to seven Raman peaks resulting from O-H bond stretching reflect the complex hydrogen bond system in the pumpellyite group structure, arising from the presence of multiple hydroxyl groups and variations in the local chemical environment due to compositional differences. | 
    
| ArticleNumber | 250401 | 
    
| Author | Mariko NAGASHIMA Daisuke NISHIO-HAMANE  | 
    
| Author_xml | – sequence: 1 fullname: Daisuke NISHIO-HAMANE organization: The Institute for Solid State Physics, the University of Tokyo – sequence: 1 fullname: Mariko NAGASHIMA organization: Division of Earth Science, Graduate School of Science and Technology for Innovation, Yamaguchi University  | 
    
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(1971) Structural relations between pumpellyite and ardennite. Acta Crystallographica, B27, 1871-1875. Momma, K. and Izumi, F. (2011) VESTA 3 for three-dimensional visualization of crystal, volumetric and morphology data. Journal of Applied Crystallography, 44, 1272-1276. Nagashima, M., Ishida, T. and Akasaka, M. (2006) Distribution of Fe among octahedral sites and its effect on the crystal structure of pumpellyite. Physics and Chemistry of Minerals, 33, 178-191. Artioli, G., Geiger, C.A. and Dapiaggi, M. (2003) The crystal chemistry of julgoldite-Fe3+ from Bombay, India, studied using synchrotron X-ray powder diffraction and 57Fe Mössbauer spectroscopy. American Mineralogist, 88, 1084-1090. Nagashima, M., Nishio-Hamane, D., Ito, S. and Tanaka, T. (2021) Ferriprehnite, Ca2Fe3+(AlSi3)O10(OH)2, an Fe3+ analogue of prehnite, from Kouragahana, Shimane Peninsula, Japan. Journal of Mineralogical and Petrological Sciences, 116, 129-139. Sheldrick, G.M. (2015) Crystal structure refinement with SHELX. Acta Crystallographica, C71, 3-8. Lafuente, B., Downs, R.T., Yang, H. and Stone, N. (2015) The powder of databases: the RRUFF project. In Highlights in Mineralogical Crystallography (Armbruster, T. and Danisi, R.M. Eds.). W. De Gruyter, Berlin, Germany, 1-30. Brigatti, M.F., Caprilli, E. and Marchesini, M. (2006) Poppiite, the V3+ end-member of the pumpellyite group: Description and crystal structure. American Mineralogist, 91, 584-588. Muñoz, M., Aguirre, L., Vergara, M., Demant, A., et al (2010) Prehnite-pumpellyite facies metamorphism in the Cenozoic Abanico Formation, Andes of central Chile (33°50′S): chemical and scale controls on mineral assemblages, reaction progress and the equilibrium state. Andean Geology, 37, 54-77. Franks, F., Ed. (1973) Water: A comprehensive treatise, vol. 2. pp. 684, Plenum, New York. Brown, I.D. and Altermatt, D. (1985) Bond-valence parameters obtained from a systematic analysis of the inorganic crystal structure database. Acta Crystallographica, B41, 244-247. Nagashima, M. and Akasaka, M. (2007) Distribution of chromium in Cr-rich pumpellyite from Sarani, Urals, Russia: a TOF neutron and X-ray Rietveld study. The Canadian Mineralogist, 45, 837-846. Tomiyoshi, S. and Takasu, A. (2010) K-Ar ages of lawsonite-bearing pelitic schists from the Sambagawa metamorphic belt in the Ise district, eastern Kii Peninsula, southeast Japan. Earth Science (Chikyu Kagaku), 64, 193-200. Gottardi, G. (1965) Die Kristallstruktur von Pumpellyit. Tschermaks Mineralogische und Petrographische Mitteilungen, 10, 115-119 (in German). Livingstone, A. (1976) Julgoldite, new data and occurrences; a second recording. Mineralogical Magazine, 40, 761-763. Nakamura, Y. (1971) Petrology of the Toba ultramafic complex, Mie Prefecture, Central Japan. Journal of Faculty of Science, University of Tokyo, Section II, 18, 1-51. 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(2022) Low-grade prehnite-pumpellyite facies metamorphism and metasomatism in basement rocks adjacent to the Permian Oslo rift: The importance of displacive reactions. Journal of Metamorphic Geology, 40, 1467-1492. Passaglia, E. and Gottardi, G. (1973) Crystal chemistry and nomenclature of pumpellyites and julgoldites. The Canadian Mineralogist, 12, 219-223. Seki, Y. (1958) Glaucophanic regional metamorphism in the Kanto Mountains, Central Japan. Japanese Journal of Geology and Geography, 29, 233-258. Moore, P.B. (1971) Julgoldite, the Fe2+-Fe3+ dominant pumpellyite. A new mineral from Långban, Sweden. Lithos, 4, 93-99. Artioli, G. and Geiger, C.A. (1994) The crystal chemistry of pumpellyite: an X-ray Rietveld refinement and 57Fe Mössbauer study. Physics and Chemistry of Minerals, 20, 443-453. Hatert, F., Pasero, M., Perchiazzi, N. and Theye, T. (2007) Pumpellyite-(Al), a new mineral from Bertrix, Belgian Ardennes. European Journal of Mineralogy, 19, 247-253. Nagashima, M., Cametti, G. and Armbruster, T. (2018a) Crystal chemistry of julgoldite, a mineral of the pumpellyite group: Re-investigation of Fe distribution and hydrogen-bonding. European Journal of Mineralogy, 30, 721-731. Allmann, R. and Donnay, G. (1973) The crystal structure of julgoldite. Mineralogical Magazine, 39, 271-281. Kano, K., Satoh, H. and Bunno, M. (1986) Iron-rich pumpellyite and prehnite from the Miocene gabbroic sills of the Shimane Peninsula, Southwest Japan. Journal of Japanese Association of Mineralogy, Petrology and Economic Geology, 81, 51-58. Nagashima, M., Iwasa, K. and Akasaka, M. (2016) Relation between occurrence and chemical compositions of prehnite in hydrothermally altered dolerite from Mitsu, Shimane Peninsula, Japan. Geoscience Reports of Shimane University, 34, 1-8 (in Japanese with English abstract). Matsubara, M., Kato, A. and Kamiya, T. (1992) Julgoldite-(Fe2+) from Kouragahana, Shimane Prefecture. 1992 Annual meeting abstract Mineralogical Society of Japan, 161 (in Japanese, title is translated by MN). Baur, H. (1974) The geometry of polyhedral distortions. Predictive relationships for the phosphate group. Acta Crystallographica, B30, 1195-1215. Deer, W.A., Howie, R.A. and Zussman, J. (1986) Rock-forming minerals. 1B (Second edition), Disilicates and ring silicates. pp. 629, Geological Society Publishing House, UK. Yoshiasa, A. and Matsumoto, T. (1985) Crystal structure refinement and crystal chemistry of pumpellyite. American Mineralogist, 70, 1011-1019. Akasaka, M., Kimura, Y., Omori, Y., Sakakibara, M., et al (1997) 57Fe Mössbauer study of pumpellyite-okhotskite-julgoldite series minerals. Mineralogy and Petrology, 61, 181-198. Uchino, T., Nakae, S. and Nakashima, R. (2017) Geology of the Toba District. Quadrangle Series, 1:50,000. pp. 141, Geological Survey of Japan, AIST (in Japanese with English abstract). Nagashima, M., Matsumoto, T., Yamada, T., Takizawa, M. and Momma, K. (2018b) Crystal chemistry of poppiite, V-analogue of pumpellyite, from the Komatsu mine, Saitama Prefecture, Japan. Journal of Mineralogical and Petrological Sciences, 113, 251-262. 22 23 24 G. Artioli (7) 1994; 20 25 26 28 29 A. Yoshiasa (42) 1985; 70 E. Passaglia (36) 1973; 12 30 31 10 32 11 33 12 34 13 35 14 15 37 16 38 17 39 18 19 M. Kováčik (21) 2011; 43 M. Muñoz (27) 2010; 37 1 2 3 4 5 6 8 9 40 41 20  | 
    
| References_xml | – reference: Franks, F., Ed. (1973) Water: A comprehensive treatise, vol. 2. pp. 684, Plenum, New York. – reference: Nagashima, M., Iwasa, K. and Akasaka, M. (2016) Relation between occurrence and chemical compositions of prehnite in hydrothermally altered dolerite from Mitsu, Shimane Peninsula, Japan. Geoscience Reports of Shimane University, 34, 1-8 (in Japanese with English abstract). – reference: Uchino, T., Nakae, S. and Nakashima, R. (2017) Geology of the Toba District. Quadrangle Series, 1:50,000. pp. 141, Geological Survey of Japan, AIST (in Japanese with English abstract). – reference: Akasaka, M., Kimura, Y., Omori, Y., Sakakibara, M., et al (1997) 57Fe Mössbauer study of pumpellyite-okhotskite-julgoldite series minerals. Mineralogy and Petrology, 61, 181-198. – reference: Brown, I.D. and Altermatt, D. (1985) Bond-valence parameters obtained from a systematic analysis of the inorganic crystal structure database. Acta Crystallographica, B41, 244-247. – reference: Muñoz, M., Aguirre, L., Vergara, M., Demant, A., et al (2010) Prehnite-pumpellyite facies metamorphism in the Cenozoic Abanico Formation, Andes of central Chile (33°50′S): chemical and scale controls on mineral assemblages, reaction progress and the equilibrium state. Andean Geology, 37, 54-77. – reference: Nagashima, M., Cametti, G. and Armbruster, T. (2018a) Crystal chemistry of julgoldite, a mineral of the pumpellyite group: Re-investigation of Fe distribution and hydrogen-bonding. European Journal of Mineralogy, 30, 721-731. – reference: Brastad, K. (1984) Julgoldite from Tafjord, Sunnmøre. Contribution to the Mineralogy of Norway, No. 67. Norsk Geologisk Tidsskrift, 3, 251-255. – reference: Shannon, R.D. (1976) Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides. Acta Crystallographica, A32, 751-767. – reference: Nagashima, M., Matsumoto, T., Yamada, T., Takizawa, M. and Momma, K. (2018b) Crystal chemistry of poppiite, V-analogue of pumpellyite, from the Komatsu mine, Saitama Prefecture, Japan. Journal of Mineralogical and Petrological Sciences, 113, 251-262. – reference: Passaglia, E. and Gottardi, G. (1973) Crystal chemistry and nomenclature of pumpellyites and julgoldites. The Canadian Mineralogist, 12, 219-223. – reference: Hamada, M., Akasaka, M., Seto, S. and Makino, K. (2010) Crystal chemistry of chromian pumpellyite from Osayama, Okayama Prefecture, Japan. American Mineralogist, 95, 1294-1304. – reference: Kováčik, M. (2011) Pumpellyite-prehnite mineral assemblage in Tatric basement and its relation to the Central Western Carpathian units. Mineralia Slovaca, 43, 263-272. – reference: Nakamura, Y. (1971) Petrology of the Toba ultramafic complex, Mie Prefecture, Central Japan. Journal of Faculty of Science, University of Tokyo, Section II, 18, 1-51. – reference: Akasaka, M., Goishi (Imaizumi), Y., Sakakibara, M. and Nakamuta, Y. (2023) The oxidation state and distribution of Fe in pumpellyite from the Northern Chichibu Belt in the Hijikawa district, western Shikoku, Japan. Mineralogical Magazine, 87, 916-934. – reference: Moore, P.B. (1971) Julgoldite, the Fe2+-Fe3+ dominant pumpellyite. A new mineral from Långban, Sweden. Lithos, 4, 93-99. – reference: Austrheim, H., Engvik, A.N., Ganerød, M., Dunkel, K.G. and Velo, M.R. (2022) Low-grade prehnite-pumpellyite facies metamorphism and metasomatism in basement rocks adjacent to the Permian Oslo rift: The importance of displacive reactions. Journal of Metamorphic Geology, 40, 1467-1492. – reference: Nagashima, M. and Akasaka, M. (2007) Distribution of chromium in Cr-rich pumpellyite from Sarani, Urals, Russia: a TOF neutron and X-ray Rietveld study. The Canadian Mineralogist, 45, 837-846. – reference: Nagashima, M., Armbruster, T. and Libowitzky, E. (2010) The hydrogen-bond system in pumpellyite. European Journal of Mineralogy, 22, 333-342. – reference: Kano, K., Satoh, H. and Bunno, M. (1986) Iron-rich pumpellyite and prehnite from the Miocene gabbroic sills of the Shimane Peninsula, Southwest Japan. Journal of Japanese Association of Mineralogy, Petrology and Economic Geology, 81, 51-58. – reference: Lafuente, B., Downs, R.T., Yang, H. and Stone, N. (2015) The powder of databases: the RRUFF project. In Highlights in Mineralogical Crystallography (Armbruster, T. and Danisi, R.M. Eds.). W. De Gruyter, Berlin, Germany, 1-30. – reference: Livingstone, A. (1976) Julgoldite, new data and occurrences; a second recording. Mineralogical Magazine, 40, 761-763. – reference: Robinson, K., Gibbs, G.V. and Ribbe, P.H. (1971) Quadratic elongation: a quantitative measure of distortion in coordination polyhedra. Science, 172, 567-570. – reference: Kasatkin, A.V., Zubkova, N.V., Chukanov, N.V., Ksenofontov, D.A., et al (2021) Unusually iron-rich julgoldite-(Fe3+) from the Karadag volcanic massif (Crimea Peninsula). Zapiski Rossiiskogo Mineralogicheskogo Obshchestva, 150, 96-112 (in Russian with English abstract). – reference: Deer, W.A., Howie, R.A. and Zussman, J. (1986) Rock-forming minerals. 1B (Second edition), Disilicates and ring silicates. pp. 629, Geological Society Publishing House, UK. – reference: Yoshiasa, A. and Matsumoto, T. (1985) Crystal structure refinement and crystal chemistry of pumpellyite. American Mineralogist, 70, 1011-1019. – reference: Sheldrick, G.M. (2015) Crystal structure refinement with SHELX. Acta Crystallographica, C71, 3-8. – reference: Artioli, G. and Geiger, C.A. (1994) The crystal chemistry of pumpellyite: an X-ray Rietveld refinement and 57Fe Mössbauer study. Physics and Chemistry of Minerals, 20, 443-453. – reference: Artioli, G., Geiger, C.A. and Dapiaggi, M. (2003) The crystal chemistry of julgoldite-Fe3+ from Bombay, India, studied using synchrotron X-ray powder diffraction and 57Fe Mössbauer spectroscopy. American Mineralogist, 88, 1084-1090. – reference: Hatert, F., Pasero, M., Perchiazzi, N. and Theye, T. (2007) Pumpellyite-(Al), a new mineral from Bertrix, Belgian Ardennes. European Journal of Mineralogy, 19, 247-253. – reference: Baur, H. (1974) The geometry of polyhedral distortions. Predictive relationships for the phosphate group. Acta Crystallographica, B30, 1195-1215. – reference: Allmann, R. and Donnay, G. (1973) The crystal structure of julgoldite. Mineralogical Magazine, 39, 271-281. – reference: Brigatti, M.F., Caprilli, E. and Marchesini, M. (2006) Poppiite, the V3+ end-member of the pumpellyite group: Description and crystal structure. American Mineralogist, 91, 584-588. – reference: Gottardi, G. 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| SubjectTerms | Cations Crystal structure Deformation Divalent cations Hydrogen bond Hydroxyl groups Julgoldite Minerals Pumpellyite Raman Single crystals Yttrium  | 
    
| Title | The crystal chemistry of pumpellyite from Sugashima and julgoldite from Kouragahana, Japan: Toward a comprehensive understanding of the crystal chemistry of pumpellyite-group minerals | 
    
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