Summary
Fe and Mn distribution in the pumpellyite group minerals (W 8 X 4 Y 8 Z 12056-n (OH) n ) has been studied by using57Fe Mössbauer spectroscopy. The studied Fe-pumpellyites, belonging to the pumpellyite-julgoldite series, were collected from two localities; metabasites in the Tokoro belt, Hokkaido, and gabbroic sills in the Shimane Peninsula, Japan. Okhotskite, an Mn3+-dominant pumpellyite group mineral, was separated from the ores of metamorphosed manganiferous iron ore deposits in the Tokoro belt.57Fe Mössbauer spectrum of Tokoro Fe-pumpellyite is composed of two Fe2+- and two Fe3+-doublets. On the basis of the single crystal structure refinements of Al-pumpellyites published so far, doublets were assigned to Fe 2+ W (IS= 1.01 andQS = 2.73 mm/s), Fe 2+ X (IS = 0.97 andQS = 3.18 mm/s), Fe 3+ X (IS = 0.29 andQS =1.37 mm/s) and Fe 3+ Y (IS = 0.36 andQS = 2.09 mm/s), whereIS is isomer shift relative to a metallic iron absorber andQS is quadrupole splitting. The Mössbauer spectrum of the Mitsu Fepumpellyite is composed of three doublets assigned to Fe 2+ X (IS= 1.14 andQS = 3.20 mm/s), Fe 3+ X (IS = 0.36 andQS =1.13 mm/s) and Fe 3+ Y (IS = 0.37 andQS= 1.93 mm/s). These assignments show strong preference of Fe3+ in the X-site. The Mössbauer spectrum of the okhotskite is composed of two doublets by Fe 3+ X (IS= 0.37 andQS = 1.13 mm/s) and Fe 3+ Y (IS = 0.42 andQS = 2.18 mm/s). The area ratio shows that Fe 3+ X :Fe 3+ Y ratio is 94:6. On the basis of chemical and Mössbauer analyses, Mn 3+ X :Mn 3+ Y ratio is given as 19:81, indicating stronger Y-site preference of Mn3+ than Fe3+, what is consistent with Jahn-Teller theory. Al, Mn3+ and Fe3+ prefer the Y-site in this order.
Zusammenfassung
Die Fe- und Mn-Verteilung in Mineralen der Pumpellyit-Gruppe (W 8 X 4 Y 8 Z 12O56-n (OH)n) wurde mittels Mössbauer-Spektroskopie studiert. Die untersuchten Fe-Pumpellyite der Pumpellyit-Julgoldit-Serie stammen von zwei verschiedenen japanischen Lokalitäten: von Metabasiten des Tokoro-Gürtels, Hokkaido, und von Gabbro-Sills der Shimane Halbinsel. Okhotskit, ein Mn3+-dominiertes Mineral der Pumpellyit-Gruppe, wurde aus Erzen einer Mn-führenden Eisenerzlagerstätte des Tokoro-Gürtels separiert. Das57Fe Mössbauer-Spektrum der Tokoro Fe-Pumpellyite zeigt zwei Fe2+- und zwei Fe3+-Doubletten. Auf Grund bisher publizierter verfeinerter Einkristall-Strukturuntersuchungen von Al-Pumpellyiten werden diese Doubletten folgendermaßen zugeordnet: Fe 2+ W (IS = 1.01 undQS = 2.73 mm/s), Fe 2+ X (IS = 0.97 undQS = 3.18 mm/s), Fe 3+ X (IS = 0.29 undQS =1.37 mm/s) und Fe 3+ Y (IS = 0.36 undQS = 2.09 mm/s).IS bezeichnet dabei die Isomer-Shift relativ zu einem metallischen Eisenabsorbenten,QS das Quadrupole-Splitting. Diese Zuordnungen belegen den bevorzugten Einbau von Fe3+ in die X-Position. Das Mössbauer-Spektrum von Okhotskit zeigt zwei Doubletten bei Fe 3+ X (IS = 0.37 undQS = 1.13 mm/s) und Fe 3+ Y (IS = 0.42 undQS = 2.18 mm/s). Das Flächenverhältnis zeigt, daß das Verhältnis Fe 3+ X :Fe 3+ Y 94:6 ist. Auf Grund der chemischen und der Mössbauer-Analysen wird das Mn 3+ X :Mn 3+ Y Verhältnis mit 19:81 angegeben. Mn3+ zeigt somit eine stärkere Präferenz für die Y-Position als Fe3+, ein Resultat, das mit der Jahn-Teller-Theorie konsistent ist. Der bevorzugte Einbau in die Y-Position ist, in dieser Reihenfolge, Al>Mn3+>Fe3+.
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References
Akasaka M, Sakakibara M, Togari K (1988) Piemontite from the manganiferous hematite ore deposits in the Tokoro Belt, Hokkaido, Japan. Mineral Petrol 38: 105–116
Akasaka M, Omori Y, Sakakibara M, Shinno I (1994) M6ssbauer parameter of Fe3+ in the X- and Y-sites in pumpellyite-julgoldite series minerals. Annual Meeting of Mineral Soc Japan, p 188 (in Japanese)
Allmann R, Donnay G (1971) Structural relations between pumpellyite and ardennite. Acta Cryst B27: 1871–1875
Artioli G, Geiger CA (1994) The crystal chemistry of pumpellyite: an X-ray Rietveld refinement and57Fe Mössbauer study. Phys Chem Minerals 20: 443–453
Artioli G, Sacchi M, Balerna A, Burattini E, Simeoni S (1991) XANES studies of Fe in pumpellyite-group minerals. N Jb Mineral Monatsh: 413–421
Artioli G, Bellotto M, Pavese A, Collins SP, Lucchetti G (1993) Resonant powder X-ray diffraction: study of Mn oxidation-state and distribution in pumpellyite minerals. First Congress of the Italian Synchrotron Radiation Society (Rome). CNR Abstract: PS-50
Artioli G, Quartieri S, Deriu A (1995) Spectroscopic data on coexisting prehnitepumpellyite and epidote-pumpellyite. Can Mineral 33: 67–75
Artioli G, Pavese A, Bellotto M, Collins SP, Lucchetti G (1996) Mn crystal chemistry in pumpellyite: a resonant-scattering powder diffraction Rietveld study using synchrotron radiation. Am Mineral 81: 603–610
Bancroft GM, Maddock AG, Burns RG (1967) Applications of the Massbauer effect to silicate mineralogy. 1. Iron silicates of known crystal structure. Geochim Cosmochim Acta 31: 2219–2240
Burns RG (1970) Mineralogical applications of crystal field theory. Cambridge University Press, Cambridge, 224pp
Coombs DS (1953) The pumpellyite mineral series. Mineral Mag 30: 113–135
Dollase WA (1973) Mössbauer spectra and iron distribution in the epidote-group minerals. Z Kristallogr 138: 41–64
Galli E, Alberti A (1969) On the crystal structure of pumpellyite. Acta Crystal B25: 2276–2281
Ghose S, Kersten M, Langer K, Rossi G, Ungaretti L (1986) Crystal field spectra and Jahn Teller effect of Mn 3+ in clinopyroxene and clinoamphiboles from India. Phys Chem Minerals 13: 291–305
Hawthorne FC (1988) Massbauer spectroscopy. In:Hawthorne FC (eds) Reviews in mineralogy, vol 18. Spectroscopic methods in mineralogy and geology. Mineralogical Society of America, Washington, pp 255–340
Ivanov OK, Arkhangel'skaya VA, Miroshnikova LO, Shilova TA (1981) Shuiskite, the chromium analogue of pumpellyite, from the Bisersk deposit, Urals. Zapiski Vses Mineral Obsh 110: 508–512 (in Russian)
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 Min Petr Econ Geol 81: 51–58
Kato A, Matsubara S, Yamamoto R (1981) Pumpellyite-(Mn 2+) from the Ochiai Mine, Yamanashi Prefecture, Japan. Bull Minèral 104: 396–399
Kimura Y, Akasaka M, Sakakibara M, Shinno I, Togari K (1995) Distribution of Fe3+ and Mn3+ in okhotskite. Geol Report Shimane Univ 14: 43–54 (in Japanese with English abstract)
Moor PB (1971) Julgoldite, the Fe e+-Fe3+ dominant pumpellyite. Lithos 4: 93–99
Palache C, Vassar HE (1925) Some minerals of the Keweenawan copper deposits: pumpellyite, a new mineral; sericite; saponite. Am Mineral 10: 412–418
Passaglia E, Gottardi G (1973) Crystal chemistry and nomenclature of pumpellyites and julgoldites. Can Mineral 12: 219–223
Pan Y, Fleet ME (1992) Vanadium-rich minerals of the pumpellyite group from the Hemlo gold deposit, Ontario. Can Mineral 30: 153–162
Robinson K, Gibbs GV, Ribbe PH (1971) Quadratic elongation, a quantitative measure of distortion in coordination polyhedra. Science 172: 567–570
Sakakibara M (1986) A newly discovered high-pressure terrane in eastern Hokkaido, Japan. J Metam Geol 4: 401–408
Sakakibara M (1991) Metamorphic petrology of the Northern Tokoro metabasites, eastern Hokkaido, Japan. J Petrol 32: 333–364
Sakakibara M, Akasaka M, Togari K (1986) Fe-pumpellyite from the Tokoro metamorphic belt. 1986 Joint Annual Meeting, p 135 (in Japanese)
Shinno I, Maeda Y (1981) A FORTRAN IV computer program LSF for analysis of Mössbauer spectra. The Reports on Earth Science College of General Education Kyushu Univ 22, pp 13–26 (in Japanese)
Shannon RD (1976) Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides. Acta Crystal A32: 751–767
Togari K, Akasaka M (1987) Okhotskite, a new mineral, an Mn3+-dominant member of the pumpellyite group, from the Kokuriki mine, Hokkaido, Japan. Mineral Mag 51: 611–614
Togari K, Akasaka M, Sakakibara M, Watanabe T (1988) Mineralogy of maganiferous iron ore deposits and chert from the Tokoro Belt, Hokkaido. Mining Geol [Spec Issue] 12: 115–126
van der Woude F (1996) Mbssbauer effect in a-Fe2O3. Phys Stat Sol 17: 417–432
Yoshiasa A, Matsumoto T (1985) Crystal structure refinement and crystal chemistry of pumpellyite. Am Mineral 70: 1011–1019
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Akasaka, M., Kimura, Y., Omori, Y. et al. 57Fe Mössbauer study of pumpellyiteokhotskite-julgoldite series minerals. Mineralogy and Petrology 61, 181–198 (1997). https://doi.org/10.1007/BF01172483
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DOI: https://doi.org/10.1007/BF01172483