Articles | Volume 35, issue 2
https://doi.org/10.5194/ejm-35-267-2023
© Author(s) 2023. This work is distributed under
the Creative Commons Attribution 4.0 License.
the Creative Commons Attribution 4.0 License.
https://doi.org/10.5194/ejm-35-267-2023
© Author(s) 2023. This work is distributed under
the Creative Commons Attribution 4.0 License.
the Creative Commons Attribution 4.0 License.
Research article
| 
06 Apr 2023
Research article |
| 06 Apr 2023
| 06 Apr 2023
Optimal Raman-scattering signal for estimating the Fe3+ content on the clinozoisite–epidote join
Mariko Nagashima
CORRESPONDING AUTHOR
Division of Earth Science, Graduate School of Sciences and Technology
for Innovation, Yamaguchi University, Yamaguchi, 753-8512, Japan
Fachbereich Erdsystemwissenschaften, Universität Hamburg, 20146 Hamburg, Germany
Boriana Mihailova
Fachbereich Erdsystemwissenschaften, Universität Hamburg, 20146 Hamburg, Germany
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Ferro-ferri-holmquistite (IMA2022-020), ideal formula ☐Li2(Fe32+Fe23+)Si8O22(OH)2, was found in albitized granite from the Iwagi islet, Ehime, Japan. It is a Fe2+Fe3+ analogue of holmquistite and belongs to the lithium subgroup amphiboles. Ferro-ferri-holmquistite occurs as blue acicular crystals typically replacing the biotite and is the product of metasomatic mineral replacement reactions by dissolution–reprecipitation processes associated with Na- and Li-rich hydrothermal fluids.
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By applying in situ high-temperature Raman spectroscopy to (OH)-- and Fe2+-bearing fluorophlogopite we show that a phonon-driven structural instability near 600 K triggers the mobilization of interlayer K+ cations, which can act as charge carriers. Above 1100 K all H+ cations delocalize and can also contribute to transport processes. Above 1300 K oxidation of Fe takes place, along with limited dehydrogenation and dehydroxylation, facilitating partial K+ leakage and structural decomposition.
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The new mineral heimite was originally discovered on the mine dumps of the Grosses Chalttal deposit, Mürtschenalp district, Glarus, Switzerland. Its relatively simple chemistry is formed by water and ions of lead, copper, arsenic, hydrogen and oxygen. The mineral's crystal structure is related to the well-known duftite, which is also observed to grow on crystals of heimite. While heimite has so far only been found in the central Alps, it is expected to occur in other copper deposits worldwide.
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Combined Raman-scattering and wavelength-dispersive electron microprobe (WD-EMP) analyses of natural biotites expanding over the whole biotite solid-solution series demonstrate that the chemical composition of the MO6 octahedra, TO4 tetrahedra, and interlayer space can be non-destructively determined by Raman spectroscopy with relative uncertainties below 8 %. The content of critical minor elements such as Ti at the octahedral site can be quantified as well with a relative error of ~ 20 %.
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Ferro-ferri-holmquistite (IMA2022-020), ideal formula ☐Li2(Fe32+Fe23+)Si8O22(OH)2, was found in albitized granite from the Iwagi islet, Ehime, Japan. It is a Fe2+Fe3+ analogue of holmquistite and belongs to the lithium subgroup amphiboles. Ferro-ferri-holmquistite occurs as blue acicular crystals typically replacing the biotite and is the product of metasomatic mineral replacement reactions by dissolution–reprecipitation processes associated with Na- and Li-rich hydrothermal fluids.
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Short summary
We provide a tool for fast preparation-free estimation of the Fe3+ content in Al–Fe3+ series epidotes by Raman spectroscopy. The peaks near 570, 600, and 1090 cm−1, originating from Si2O7 vibrations, strongly correlated with Fe content, and all three signals are well resolved in a random orientation. Among them, the 570 cm−1 peak is the sharpest and easily recognized. Hence, the linear trend, ω570 = 577.1(3) − 12.7(4)x, gives highly reliable Fe content, x, with accuracy ± 0.04 Fe3+ apfu.
We provide a tool for fast preparation-free estimation of the Fe3+ content in Al–Fe3+ series...
