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The oxidation state and distribution of Fe in pumpellyite from the Northern Chichibu Belt in the Hijikawa district, western Shikoku, Japan

Published online by Cambridge University Press:  16 October 2023

Masahide Akasaka Open the ORCID record for Masahide Akasaka [Opens in a new window] ,
Yumi Goishi (Imaizumi) ,
Masayuki Sakakibara  and
Yoshihiro Nakamuta
Masahide Akasaka*
Affiliation:
Department of Geoscience, Interdisciplinary Graduate School of Science and Engineering, Shimane University, Nishikawatsu 1060, Matsue 690-8504, Japan
Yumi Goishi (Imaizumi)
Affiliation:
Department of Geoscience, Interdisciplinary Graduate School of Science and Engineering, Shimane University, Nishikawatsu 1060, Matsue 690-8504, Japan SHIBAURA ENGINEERING WORKS Co., Ltd., 2-5-1 Kasama, Sakae-ku, Yokohama 247-0006, Japan
Masayuki Sakakibara
Affiliation:
Department of Regional Resource Management, Faculty of Collaborative Regional Innovation, Ehime University, 2-5 Bunkyo-Cho, Matsuyama 790-8577, Japan
Yoshihiro Nakamuta
Affiliation:
Kyushu University Museum, Kyushu University, Hakozaki, Higashi-ku, Fukuoka 812-8581, Japan
*
Corresponding author: Masahide Akasaka; Email: [email protected]
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Abstract

Intracrystalline distribution of ferrous and ferric iron within pumpellyites (VIIW8VIX4VIY8IVZ12O56–n(OH)n, Z = 1) from low-grade metamorphic green rocks of the Kanogawa unit in the Northern Chichibu Belt, Hijikawa district, western Shikoku, Japan, was investigated using electron microprobe analysis, X-ray Rietveld refinement, and 57Fe Mössbauer spectroscopic analysis to verify the regularity of the distribution of Fe within the octahedral X and Y sites in pumpellyite and its effect on the pumpellyite structure. Two Fe-rich pumpellyite samples, labelled CLW and CHG, with average total Fe2O3 of 10.01±1.69 and 16.07±1.08 wt.%, respectively, were separated from the rock samples. The site occupancies at the X and Y sites in the CLW and CHG pumpellyites, refined using powder X-ray diffraction data, are X[Mg0.298Fe0.298(5)Al0.405]Y[Fe0.191Al0.809] and X[Mg0.244Fe0.42(1)Al0.34]Y[Fe0.32Al0.68], respectively. The Fe2+:Fe3+ ratio of the CLW pumpellyite, determined using Mössbauer spectroscopy, is 12(1):88(3). By combining the average chemical composition data, the site occupancies at the X and Y sites, and the Fe2+:Fe3+ ratio of the CLW pumpellyite, the chemical formulae of CLW and CHG pumpellyites are constructed as (Ca7.96K0.02Na0.01)Σ7.99(Mg1.19Mn2+0.09Fe2+0.39Fe3+0.71Al1.62)Σ4.00(Al6.47Fe3+1.50V0.02Ti0.01)Σ8.00Si12.26O43.33(OH)12.67 and (Ca8.01K0.01)Σ8.02(Mg0.97Mn2+0.02Fe2+0.63Fe3+1.03Al1.19)Σ4.01(Al5.44Fe3+2.55V0.01)Σ8.00Si12.02O42.69OH)13.31, respectively, implying that the proper name of both pumpellyites is pumpellyite-(Al). The intracrystalline distribution coefficients of Fe3+ versus Al between the X and Y sites, KD = (Fe3+/Al)X/(Fe3+/Al)Y, are 1.62 and 1.90 for the CLW and CHG pumpellyites, respectively, implying stronger X-site preference of Fe3+ than Al3+. In the CHG pumpellyite, where the Fe contents at the X and Y sites are higher than in the CLW pumpellyite, the mean <X–O> and <Y–O> distances are 2.06 and 1.98 Å, respectively, which are larger than <X–O> = 2.040 and <Y–O> = 1.944 Å in the CLW pumpellyite. The unit-cell parameters of the CHG pumpellyite are a = 8.8672(3), b = 5.9562(2), c = 19.1899(6) Å, β = 97.473(2)° with V = 1004.9(2) Å3 and are larger than those of the CLW pumpellyite, a = 8.8456(4), b = 5.9393(2), c = 19.1613(8) Å, β = 97.461(3)° with V = 998.14(7) Å3.

Keywords

Pumpellyite-(Al)Fe in pumpellyite and julgolditenorthern Chichibu belt in ShikokuMössbauer spectroscopic analysisX-ray Rietveld analysiscrystal chemistry
Type
Article
Information
Mineralogical Magazine , Volume 87 , Issue 6 , December 2023 , pp. 916 - 934
Copyright
Copyright © The Author(s), 2023. Published by Cambridge University Press on behalf of The Mineralogical Society of the United Kingdom and Ireland

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Footnotes

Associate Editor: Runliang Zhu

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