Articles | Volume 35, issue 1
https://doi.org/10.5194/ejm-35-105-2023
© Author(s) 2023. This work is distributed under
the Creative Commons Attribution 4.0 License.
the Creative Commons Attribution 4.0 License.
Special issue:
https://doi.org/10.5194/ejm-35-105-2023
© Author(s) 2023. This work is distributed under
the Creative Commons Attribution 4.0 License.
the Creative Commons Attribution 4.0 License.
Research article
| 
16 Feb 2023
Research article |
| 16 Feb 2023
| 16 Feb 2023
Effect of Fe–Fe interactions and X-site vacancy ordering on the OH-stretching spectrum of foitite
Etienne Balan
CORRESPONDING AUTHOR
Sorbonne Université, CNRS, MNHN, IRD, Institut de Minéralogie, de Physique des Matériaux et de Cosmochimie (IMPMC), 4 place Jussieu, CEDEX 05, 75252 Paris, France
Guillaume Radtke
CORRESPONDING AUTHOR
Sorbonne Université, CNRS, MNHN, IRD, Institut de Minéralogie, de Physique des Matériaux et de Cosmochimie (IMPMC), 4 place Jussieu, CEDEX 05, 75252 Paris, France
Chloé Fourdrin
Laboratoire Géomatériaux et Environnement, Université Gustave Eiffel, 2 allée du promontoire, 93160 Noisy-le-Grand, France
Lorenzo Paulatto
Sorbonne Université, CNRS, MNHN, IRD, Institut de Minéralogie, de Physique des Matériaux et de Cosmochimie (IMPMC), 4 place Jussieu, CEDEX 05, 75252 Paris, France
Heinrich A. Horn
Centro de Pesquisa Professor Manoel Teixeira da Costa, Departamento de Geologia, Universidade Federal de Minas Gerais (UFMG), Belo Horizonte, Brazil
Yves Fuchs
Laboratoire Géomatériaux et Environnement, Université Gustave Eiffel, 2 allée du promontoire, 93160 Noisy-le-Grand, France
deceased, 18 December 2022
Related authors
Michael C. Jollands, Shiyun Jin, Martial Curti, Maxime Guillaumet, Keevin Béneut, Paola Giura, and Etienne Balan
Eur. J. Mineral., 35, 873–890, https://doi.org/10.5194/ejm-35-873-2023, https://doi.org/10.5194/ejm-35-873-2023, 2023
Short summary
Short summary
The infrared spectrum of hydrous defects in corundum is routinely used in gemology, but the assignment of absorption bands to specific defects remains elusive. Here, we theoretically study selected defects and compare the results with available experimental data. The main results are the assignment of the
3161 cm−1 seriesto OH groups associated with Fe2+ ions and the interpretation of bands below 2700 cm−1 in corundum containing divalent cations in terms of overtones of OH bending modes.
Etienne Balan, Lorenzo Paulatto, Qianyu Deng, Keevin Béneut, Maxime Guillaumet, and Benoît Baptiste
Eur. J. Mineral., 34, 627–643, https://doi.org/10.5194/ejm-34-627-2022, https://doi.org/10.5194/ejm-34-627-2022, 2022
Short summary
Short summary
The near-infrared spectra of hydrous minerals involve OH stretching vibrations, but their interpretation is not straightforward due to anharmonicity and vibrational coupling. We analyze the spectra of well-ordered samples of talc, brucite and lizardite to better assess the various factors contributing to the absorption bands. The results clarify the relations between the overtone spectra and their fundamental counterparts and provide a sound interpretation of the two-phonon combination bands.
Yves Fuchs, Chloé Fourdrin, and Etienne Balan
Eur. J. Mineral., 34, 239–251, https://doi.org/10.5194/ejm-34-239-2022, https://doi.org/10.5194/ejm-34-239-2022, 2022
Short summary
Short summary
Information about the local structure of tourmaline-group minerals can be obtained from the characteristic OH stretching bands in their vibrational spectra. However, their assignment to specific atomic-scale environments is debated. We address this question theoretically by investigating a series of dravite models. Our results support a local role of cationic occupancies in determining the OH stretching frequencies and bring constraints for the interpretation of the vibrational spectra.
Emmanuel Fritsch, Etienne Balan, Sabine Petit, and Farid Juillot
Eur. J. Mineral., 33, 743–763, https://doi.org/10.5194/ejm-33-743-2021, https://doi.org/10.5194/ejm-33-743-2021, 2021
Short summary
Short summary
The study presents and discusses mid- and near-infrared spectra of three Mg–Ni mineral series (serpentine-like and talc-like minerals, sepiolite) commonly found in reactivated faults and sequences of clay infillings of the New Caledonian Ni-silicate deposits. This spectroscopic study sheds light on the nature of the residual mineral phases found in the clay infillings (serpentine-like minerals) and reveals the aptitude of the newly formed minerals (talc-like minerals and sepiolite) to store Ni.
Etienne Balan, Emmanuel Fritsch, Guillaume Radtke, Lorenzo Paulatto, Farid Juillot, Fabien Baron, and Sabine Petit
Eur. J. Mineral., 33, 647–657, https://doi.org/10.5194/ejm-33-647-2021, https://doi.org/10.5194/ejm-33-647-2021, 2021
Short summary
Short summary
Interpretation of vibrational spectra of serpentines is complexified by the common occurrence of divalent and trivalent cationic impurities at tetrahedral and octahedral sites. We theoretically investigate the effect of Fe and Al on the vibrational properties of lizardite, focusing on the OH stretching modes. The results allow us to disentangle the specific effects related to the valence and coordination states of the impurities, supporting a detailed interpretation of the experimental spectra.
Emmanuel Fritsch, Etienne Balan, Sabine Petit, and Farid Juillot
Eur. J. Mineral., 33, 447–462, https://doi.org/10.5194/ejm-33-447-2021, https://doi.org/10.5194/ejm-33-447-2021, 2021
Short summary
Short summary
The study provides new insights into the OH stretching vibrations of serpentine species (lizardite, chrysotile, antigorite) encountered in veins of peridotite. A combination of infrared spectroscopy in the mid-infrared and near-infrared ranges and Raman spectroscopy enabled us to interpret most of the observed bands in the fundamental and first overtone regions of the spectra and to propose consistent spectral decomposition and assignment of the OH stretching bands for the serpentine species.
Etienne Balan, Emmanuel Fritsch, Guillaume Radtke, Lorenzo Paulatto, Farid Juillot, and Sabine Petit
Eur. J. Mineral., 33, 389–400, https://doi.org/10.5194/ejm-33-389-2021, https://doi.org/10.5194/ejm-33-389-2021, 2021
Short summary
Short summary
The infrared absorption spectrum of an antigorite sample, an important serpentine-group mineral, is compared to its theoretical counterpart computed at the density functional level. The model reproduces most of the observed bands, supporting their assignment to specific vibrational modes. The results provide robust interpretations of the significant differences observed between the antigorite spectrum and that of lizardite, the more symmetric serpentine variety.
Etienne Balan, Emmanuel Fritsch, Farid Juillot, Thierry Allard, and Sabine Petit
Eur. J. Mineral., 33, 209–220, https://doi.org/10.5194/ejm-33-209-2021, https://doi.org/10.5194/ejm-33-209-2021, 2021
Short summary
Short summary
The OH overtone bands of kaolinite- and serpentine-group minerals observed in their near-infrared (NIR) spectra are widely used but their relation to stretching modes involving coupled OH groups is uncertain. Here, we map a molecular model of harmonically coupled anharmonic oscillators on the spectroscopic properties of 1:1 phyllosilicates. This makes it possible to interpret most of the observed bands and support the assignment of some of them to cationic substitutions in serpentines.
Etienne Balan, Lorenzo Paulatto, Jia Liu, and Jannick Ingrin
Eur. J. Mineral., 32, 505–520, https://doi.org/10.5194/ejm-32-505-2020, https://doi.org/10.5194/ejm-32-505-2020, 2020
Short summary
Short summary
The atomic-scale geometry of hydrous defects in diopside is still imperfectly known despite their contribution to the Earth's water cycle. Their OH-stretching vibrations lead to a variety of infrared absorption bands. Low-temperature infrared spectroscopy makes it possible to resolve additional bands in the spectra of gem-quality natural samples. Theoretical results obtained at the density functional theory level support the assignment of the observed bands to specific atomic-scale models.
Etienne Balan
Eur. J. Mineral., 32, 457–467, https://doi.org/10.5194/ejm-32-457-2020, https://doi.org/10.5194/ejm-32-457-2020, 2020
Short summary
Short summary
Corundum is an important oxide mineral which can contain low amounts of hydrogen-bearing structural defects. These defects are observed by infrared spectroscopy, but their atomic-scale geometry is still uncertain. Here, a theoretical approach makes it possible to relate most of the observed infrared bands to specific atomic configurations, highlighting the key role of other chemical impurities and defect clustering in the high-temperature incorporation of hydrogen in corundum.
Michael C. Jollands, Marc Blanchard, and Etienne Balan
Eur. J. Mineral., 32, 311–323, https://doi.org/10.5194/ejm-32-311-2020, https://doi.org/10.5194/ejm-32-311-2020, 2020
Short summary
Short summary
Quartz is a very common form of almost pure silica. It can contain a small concentration of hydrogen-bearing defects whose nature is still debated. Here, we use a theoretical approach to unravel the atomic-scale geometry of these defects. Our findings help explain some important quartz properties.
Michael C. Jollands, Shiyun Jin, Martial Curti, Maxime Guillaumet, Keevin Béneut, Paola Giura, and Etienne Balan
Eur. J. Mineral., 35, 873–890, https://doi.org/10.5194/ejm-35-873-2023, https://doi.org/10.5194/ejm-35-873-2023, 2023
Short summary
Short summary
The infrared spectrum of hydrous defects in corundum is routinely used in gemology, but the assignment of absorption bands to specific defects remains elusive. Here, we theoretically study selected defects and compare the results with available experimental data. The main results are the assignment of the
3161 cm−1 seriesto OH groups associated with Fe2+ ions and the interpretation of bands below 2700 cm−1 in corundum containing divalent cations in terms of overtones of OH bending modes.
Etienne Balan, Lorenzo Paulatto, Qianyu Deng, Keevin Béneut, Maxime Guillaumet, and Benoît Baptiste
Eur. J. Mineral., 34, 627–643, https://doi.org/10.5194/ejm-34-627-2022, https://doi.org/10.5194/ejm-34-627-2022, 2022
Short summary
Short summary
The near-infrared spectra of hydrous minerals involve OH stretching vibrations, but their interpretation is not straightforward due to anharmonicity and vibrational coupling. We analyze the spectra of well-ordered samples of talc, brucite and lizardite to better assess the various factors contributing to the absorption bands. The results clarify the relations between the overtone spectra and their fundamental counterparts and provide a sound interpretation of the two-phonon combination bands.
Yves Fuchs, Chloé Fourdrin, and Etienne Balan
Eur. J. Mineral., 34, 239–251, https://doi.org/10.5194/ejm-34-239-2022, https://doi.org/10.5194/ejm-34-239-2022, 2022
Short summary
Short summary
Information about the local structure of tourmaline-group minerals can be obtained from the characteristic OH stretching bands in their vibrational spectra. However, their assignment to specific atomic-scale environments is debated. We address this question theoretically by investigating a series of dravite models. Our results support a local role of cationic occupancies in determining the OH stretching frequencies and bring constraints for the interpretation of the vibrational spectra.
Emmanuel Fritsch, Etienne Balan, Sabine Petit, and Farid Juillot
Eur. J. Mineral., 33, 743–763, https://doi.org/10.5194/ejm-33-743-2021, https://doi.org/10.5194/ejm-33-743-2021, 2021
Short summary
Short summary
The study presents and discusses mid- and near-infrared spectra of three Mg–Ni mineral series (serpentine-like and talc-like minerals, sepiolite) commonly found in reactivated faults and sequences of clay infillings of the New Caledonian Ni-silicate deposits. This spectroscopic study sheds light on the nature of the residual mineral phases found in the clay infillings (serpentine-like minerals) and reveals the aptitude of the newly formed minerals (talc-like minerals and sepiolite) to store Ni.
Laure Gatuingt, Stéphanie Rossano, Jean-Didier Mertz, Chloé Fourdrin, Olivier Rozenbaum, Quentin Lemasson, Solenn Reguer, Nicolas Trcera, and Bruno Lanson
Eur. J. Mineral., 33, 687–702, https://doi.org/10.5194/ejm-33-687-2021, https://doi.org/10.5194/ejm-33-687-2021, 2021
Short summary
Short summary
Dark patinas rich in manganese (Mn) developed on several sandstones of the Lunéville château (France) contrasting with the general yellow color of the building. The characterization of the Mn compounds in the patinas, but also in the building stones, allowed us to propose a model for the patina formation based on the dissolution of the Mn phases initially present in the stone bulks. The results obtained in this study might enlighten processes occurring on other buildings or in natural settings.
Etienne Balan, Emmanuel Fritsch, Guillaume Radtke, Lorenzo Paulatto, Farid Juillot, Fabien Baron, and Sabine Petit
Eur. J. Mineral., 33, 647–657, https://doi.org/10.5194/ejm-33-647-2021, https://doi.org/10.5194/ejm-33-647-2021, 2021
Short summary
Short summary
Interpretation of vibrational spectra of serpentines is complexified by the common occurrence of divalent and trivalent cationic impurities at tetrahedral and octahedral sites. We theoretically investigate the effect of Fe and Al on the vibrational properties of lizardite, focusing on the OH stretching modes. The results allow us to disentangle the specific effects related to the valence and coordination states of the impurities, supporting a detailed interpretation of the experimental spectra.
Emmanuel Fritsch, Etienne Balan, Sabine Petit, and Farid Juillot
Eur. J. Mineral., 33, 447–462, https://doi.org/10.5194/ejm-33-447-2021, https://doi.org/10.5194/ejm-33-447-2021, 2021
Short summary
Short summary
The study provides new insights into the OH stretching vibrations of serpentine species (lizardite, chrysotile, antigorite) encountered in veins of peridotite. A combination of infrared spectroscopy in the mid-infrared and near-infrared ranges and Raman spectroscopy enabled us to interpret most of the observed bands in the fundamental and first overtone regions of the spectra and to propose consistent spectral decomposition and assignment of the OH stretching bands for the serpentine species.
Etienne Balan, Emmanuel Fritsch, Guillaume Radtke, Lorenzo Paulatto, Farid Juillot, and Sabine Petit
Eur. J. Mineral., 33, 389–400, https://doi.org/10.5194/ejm-33-389-2021, https://doi.org/10.5194/ejm-33-389-2021, 2021
Short summary
Short summary
The infrared absorption spectrum of an antigorite sample, an important serpentine-group mineral, is compared to its theoretical counterpart computed at the density functional level. The model reproduces most of the observed bands, supporting their assignment to specific vibrational modes. The results provide robust interpretations of the significant differences observed between the antigorite spectrum and that of lizardite, the more symmetric serpentine variety.
Etienne Balan, Emmanuel Fritsch, Farid Juillot, Thierry Allard, and Sabine Petit
Eur. J. Mineral., 33, 209–220, https://doi.org/10.5194/ejm-33-209-2021, https://doi.org/10.5194/ejm-33-209-2021, 2021
Short summary
Short summary
The OH overtone bands of kaolinite- and serpentine-group minerals observed in their near-infrared (NIR) spectra are widely used but their relation to stretching modes involving coupled OH groups is uncertain. Here, we map a molecular model of harmonically coupled anharmonic oscillators on the spectroscopic properties of 1:1 phyllosilicates. This makes it possible to interpret most of the observed bands and support the assignment of some of them to cationic substitutions in serpentines.
Etienne Balan, Lorenzo Paulatto, Jia Liu, and Jannick Ingrin
Eur. J. Mineral., 32, 505–520, https://doi.org/10.5194/ejm-32-505-2020, https://doi.org/10.5194/ejm-32-505-2020, 2020
Short summary
Short summary
The atomic-scale geometry of hydrous defects in diopside is still imperfectly known despite their contribution to the Earth's water cycle. Their OH-stretching vibrations lead to a variety of infrared absorption bands. Low-temperature infrared spectroscopy makes it possible to resolve additional bands in the spectra of gem-quality natural samples. Theoretical results obtained at the density functional theory level support the assignment of the observed bands to specific atomic-scale models.
Etienne Balan
Eur. J. Mineral., 32, 457–467, https://doi.org/10.5194/ejm-32-457-2020, https://doi.org/10.5194/ejm-32-457-2020, 2020
Short summary
Short summary
Corundum is an important oxide mineral which can contain low amounts of hydrogen-bearing structural defects. These defects are observed by infrared spectroscopy, but their atomic-scale geometry is still uncertain. Here, a theoretical approach makes it possible to relate most of the observed infrared bands to specific atomic configurations, highlighting the key role of other chemical impurities and defect clustering in the high-temperature incorporation of hydrogen in corundum.
Michael C. Jollands, Marc Blanchard, and Etienne Balan
Eur. J. Mineral., 32, 311–323, https://doi.org/10.5194/ejm-32-311-2020, https://doi.org/10.5194/ejm-32-311-2020, 2020
Short summary
Short summary
Quartz is a very common form of almost pure silica. It can contain a small concentration of hydrogen-bearing defects whose nature is still debated. Here, we use a theoretical approach to unravel the atomic-scale geometry of these defects. Our findings help explain some important quartz properties.
Related subject area
Spectroscopic methods applied to minerals
Near-infrared signature of hydrothermal opal: a case study of Icelandic silica sinters
Vibrational properties of OH groups associated with divalent cations in corundum (α-Al2O3)
The effect of chemical variability and weathering on Raman spectra of enargite and fahlore
OH incorporation and retention in eclogite-facies garnets from the Zermatt–Saas area (Switzerland) and their contribution to the deep water cycle
Optimal Raman-scattering signal for estimating the Fe3+ content on the clinozoisite–epidote join
A framework for quantitative in situ evaluation of coupled substitutions between H+ and trace elements in natural rutile
Molecular overtones and two-phonon combination bands in the near-infrared spectra of talc, brucite and lizardite
Non-destructive determination of the biotite crystal chemistry using Raman spectroscopy: how far we can go?
Crystallographic orientation mapping of lizardite serpentinite by Raman spectroscopy
The effect of Co substitution on the Raman spectra of pyrite: potential as an assaying tool
Theoretical OH stretching vibrations in dravite
First-principles modeling of the infrared spectrum of Fe- and Al-bearing lizardite
Structural, textural, and chemical controls on the OH stretching vibrations in serpentine-group minerals
The intracrystalline microstructure of Monte Fico lizardite, by optics, μ-Raman spectroscopy and TEM
First-principles modeling of the infrared spectrum of antigorite
A Raman spectroscopic study of the natural carbonophosphates Na3MCO3PO4 (M is Mn, Fe, and Mg)
Local mode interpretation of the OH overtone spectrum of 1:1 phyllosilicates
Low-temperature infrared spectrum and atomic-scale structure of hydrous defects in diopside
In situ micro-FTIR spectroscopic investigations of synthetic ammonium phengite under pressure and temperature
Theoretical infrared spectra of OH defects in corundum (α-Al2O3)
Maxime Pineau, Boris Chauviré, and Benjamin Rondeau
Eur. J. Mineral., 35, 949–967, https://doi.org/10.5194/ejm-35-949-2023, https://doi.org/10.5194/ejm-35-949-2023, 2023
Short summary
Short summary
We study Icelandic silica sinter samples formed in hot-spring environments to evaluate the effect of both temperature and microstructure on the spectral properties of hydrothermal opal. We show that spectral changes can be related to different parameters such as fluid temperatures, hydrodynamics, microbial activity, and silica micro-textures, which are specific to their environment of formation within hot-spring geothermal contexts.
Michael C. Jollands, Shiyun Jin, Martial Curti, Maxime Guillaumet, Keevin Béneut, Paola Giura, and Etienne Balan
Eur. J. Mineral., 35, 873–890, https://doi.org/10.5194/ejm-35-873-2023, https://doi.org/10.5194/ejm-35-873-2023, 2023
Short summary
Short summary
The infrared spectrum of hydrous defects in corundum is routinely used in gemology, but the assignment of absorption bands to specific defects remains elusive. Here, we theoretically study selected defects and compare the results with available experimental data. The main results are the assignment of the
3161 cm−1 seriesto OH groups associated with Fe2+ ions and the interpretation of bands below 2700 cm−1 in corundum containing divalent cations in terms of overtones of OH bending modes.
Khulan Berkh, Juraj Majzlan, Jeannet A. Meima, Jakub Plášil, and Dieter Rammlmair
Eur. J. Mineral., 35, 737–754, https://doi.org/10.5194/ejm-35-737-2023, https://doi.org/10.5194/ejm-35-737-2023, 2023
Short summary
Short summary
Since As is detrimental to the environment, the As content of ores should be reduced before it is released into the atmosphere through a smelting process. Thus, Raman spectra of typical As minerals were investigated, and these can be used in the industrial removal of As-rich ores prior to the ore beneficiation. An additional objective of our study was an investigation of the secondary products of enargite weathering. They play a decisive role in the release or retainment of As in the waste form.
Julien Reynes, Jörg Hermann, Pierre Lanari, and Thomas Bovay
Eur. J. Mineral., 35, 679–701, https://doi.org/10.5194/ejm-35-679-2023, https://doi.org/10.5194/ejm-35-679-2023, 2023
Short summary
Short summary
Garnet is a high-pressure mineral that may incorporate very small amounts of water in its structure (tens to hundreds of micrograms per gram H2O). In this study, we show, based on analysis and modelling, that it can transport up to several hundred micrograms per gram of H2O at depths over 80 km in a subduction zone. The analysis of garnet from the various rock types present in a subducted slab allowed us to estimate the contribution of garnet in the deep cycling of water in the earth.
Mariko Nagashima and Boriana Mihailova
Eur. J. Mineral., 35, 267–283, https://doi.org/10.5194/ejm-35-267-2023, https://doi.org/10.5194/ejm-35-267-2023, 2023
Short summary
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.
Mona Lueder, Renée Tamblyn, and Jörg Hermann
Eur. J. Mineral., 35, 243–265, https://doi.org/10.5194/ejm-35-243-2023, https://doi.org/10.5194/ejm-35-243-2023, 2023
Short summary
Short summary
Although rutile does not have water in its chemical formula, it can contain trace amounts. We applied a new measurement protocol to study water incorporation into rutile from eight geological environments. H2O in natural rutile can be linked to six crystal defects, most importantly to Ti3+ and Fe3+. Quantifying the H2O in the individual defects can help us understand relationships of trace elements in rutile and might give us valuable information on the conditions under which the rock formed.
Etienne Balan, Lorenzo Paulatto, Qianyu Deng, Keevin Béneut, Maxime Guillaumet, and Benoît Baptiste
Eur. J. Mineral., 34, 627–643, https://doi.org/10.5194/ejm-34-627-2022, https://doi.org/10.5194/ejm-34-627-2022, 2022
Short summary
Short summary
The near-infrared spectra of hydrous minerals involve OH stretching vibrations, but their interpretation is not straightforward due to anharmonicity and vibrational coupling. We analyze the spectra of well-ordered samples of talc, brucite and lizardite to better assess the various factors contributing to the absorption bands. The results clarify the relations between the overtone spectra and their fundamental counterparts and provide a sound interpretation of the two-phonon combination bands.
Stylianos Aspiotis, Jochen Schlüter, Günther J. Redhammer, and Boriana Mihailova
Eur. J. Mineral., 34, 573–590, https://doi.org/10.5194/ejm-34-573-2022, https://doi.org/10.5194/ejm-34-573-2022, 2022
Short summary
Short summary
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 %.
Matthew S. Tarling, Matteo Demurtas, Steven A. F. Smith, Jeremy S. Rooney, Marianne Negrini, Cecilia Viti, Jasmine R. Petriglieri, and Keith C. Gordon
Eur. J. Mineral., 34, 285–300, https://doi.org/10.5194/ejm-34-285-2022, https://doi.org/10.5194/ejm-34-285-2022, 2022
Short summary
Short summary
Rocks containing the serpentine mineral lizardite occur in many tectonic settings. Knowing the crystal orientation of lizardite in these rocks tells us how they deform and gives insights into their physical properties. The crystal orientation of lizardite is challenging to obtain using standard techniques. To overcome this challenge, we developed a method using Raman spectroscopy to map the crystal orientation of lizardite with minimal preparation on standard thin sections.
Khulan Berkh and Dieter Rammlmair
Eur. J. Mineral., 34, 259–274, https://doi.org/10.5194/ejm-34-259-2022, https://doi.org/10.5194/ejm-34-259-2022, 2022
Short summary
Short summary
Common energy dispersive methods cannot accurately analyze low concentrations of cobalt in pyrite due to the overlapping of cobalt and iron peaks. The Raman method, on the other hand, has been shown to be very sensitive to a trace amount of cobalt. In addition, it can be applied on a rough surface, does not require a vacuum chamber, and operates with a laser instead of X-rays. Thus, Raman has the potential to be used as an assaying tool for Co-bearing pyrite.
Yves Fuchs, Chloé Fourdrin, and Etienne Balan
Eur. J. Mineral., 34, 239–251, https://doi.org/10.5194/ejm-34-239-2022, https://doi.org/10.5194/ejm-34-239-2022, 2022
Short summary
Short summary
Information about the local structure of tourmaline-group minerals can be obtained from the characteristic OH stretching bands in their vibrational spectra. However, their assignment to specific atomic-scale environments is debated. We address this question theoretically by investigating a series of dravite models. Our results support a local role of cationic occupancies in determining the OH stretching frequencies and bring constraints for the interpretation of the vibrational spectra.
Etienne Balan, Emmanuel Fritsch, Guillaume Radtke, Lorenzo Paulatto, Farid Juillot, Fabien Baron, and Sabine Petit
Eur. J. Mineral., 33, 647–657, https://doi.org/10.5194/ejm-33-647-2021, https://doi.org/10.5194/ejm-33-647-2021, 2021
Short summary
Short summary
Interpretation of vibrational spectra of serpentines is complexified by the common occurrence of divalent and trivalent cationic impurities at tetrahedral and octahedral sites. We theoretically investigate the effect of Fe and Al on the vibrational properties of lizardite, focusing on the OH stretching modes. The results allow us to disentangle the specific effects related to the valence and coordination states of the impurities, supporting a detailed interpretation of the experimental spectra.
Emmanuel Fritsch, Etienne Balan, Sabine Petit, and Farid Juillot
Eur. J. Mineral., 33, 447–462, https://doi.org/10.5194/ejm-33-447-2021, https://doi.org/10.5194/ejm-33-447-2021, 2021
Short summary
Short summary
The study provides new insights into the OH stretching vibrations of serpentine species (lizardite, chrysotile, antigorite) encountered in veins of peridotite. A combination of infrared spectroscopy in the mid-infrared and near-infrared ranges and Raman spectroscopy enabled us to interpret most of the observed bands in the fundamental and first overtone regions of the spectra and to propose consistent spectral decomposition and assignment of the OH stretching bands for the serpentine species.
Giancarlo Capitani, Roberto Compagnoni, Roberto Cossio, Serena Botta, and Marcello Mellini
Eur. J. Mineral., 33, 425–432, https://doi.org/10.5194/ejm-33-425-2021, https://doi.org/10.5194/ejm-33-425-2021, 2021
Short summary
Short summary
Unusually large lizardite (Lz) crystals from Monte Fico serpentinites, Elba (Mellini and Viti, 1994), have allowed several subsequent studies. During a µ-Raman study of serpentine minerals (Compagnoni et al., 2021), the careful microscopic examination of this Lz showed
spongymicrostructure. TEM observations confirmed that the Lz hosts voids, filled with chrysotile and polygonal serpentine; their mutual relationships indicate that Lz grew up with a skeletal habit and fibres epitactically.
Etienne Balan, Emmanuel Fritsch, Guillaume Radtke, Lorenzo Paulatto, Farid Juillot, and Sabine Petit
Eur. J. Mineral., 33, 389–400, https://doi.org/10.5194/ejm-33-389-2021, https://doi.org/10.5194/ejm-33-389-2021, 2021
Short summary
Short summary
The infrared absorption spectrum of an antigorite sample, an important serpentine-group mineral, is compared to its theoretical counterpart computed at the density functional level. The model reproduces most of the observed bands, supporting their assignment to specific vibrational modes. The results provide robust interpretations of the significant differences observed between the antigorite spectrum and that of lizardite, the more symmetric serpentine variety.
Evgeniy Nikolaevich Kozlov, Ekaterina Nikolaevna Fomina, Vladimir Nikolaevich Bocharov, Mikhail Yurievich Sidorov, Natalia Sergeevna Vlasenko, and Vladimir Vladimirovich Shilovskikh
Eur. J. Mineral., 33, 283–297, https://doi.org/10.5194/ejm-33-283-2021, https://doi.org/10.5194/ejm-33-283-2021, 2021
Short summary
Short summary
Carbonophosphates (sidorenkite, bonshtedtite, and bradleyite) with the general formula Na3MCO3PO4 (M is Mn, Fe, and Mg) are often found in inclusions of carbonatite and kimberlite minerals. This article presents the results of Raman spectroscopic study and a simple algorithm for diagnosing mineral phases of the carbonophosphate group. This work may be of interest both to researchers of carbonatites and/or kimberlites and to a wide range of specialists in the field of Raman spectroscopy.
Etienne Balan, Emmanuel Fritsch, Farid Juillot, Thierry Allard, and Sabine Petit
Eur. J. Mineral., 33, 209–220, https://doi.org/10.5194/ejm-33-209-2021, https://doi.org/10.5194/ejm-33-209-2021, 2021
Short summary
Short summary
The OH overtone bands of kaolinite- and serpentine-group minerals observed in their near-infrared (NIR) spectra are widely used but their relation to stretching modes involving coupled OH groups is uncertain. Here, we map a molecular model of harmonically coupled anharmonic oscillators on the spectroscopic properties of 1:1 phyllosilicates. This makes it possible to interpret most of the observed bands and support the assignment of some of them to cationic substitutions in serpentines.
Etienne Balan, Lorenzo Paulatto, Jia Liu, and Jannick Ingrin
Eur. J. Mineral., 32, 505–520, https://doi.org/10.5194/ejm-32-505-2020, https://doi.org/10.5194/ejm-32-505-2020, 2020
Short summary
Short summary
The atomic-scale geometry of hydrous defects in diopside is still imperfectly known despite their contribution to the Earth's water cycle. Their OH-stretching vibrations lead to a variety of infrared absorption bands. Low-temperature infrared spectroscopy makes it possible to resolve additional bands in the spectra of gem-quality natural samples. Theoretical results obtained at the density functional theory level support the assignment of the observed bands to specific atomic-scale models.
Nada Abdel-Hak, Bernd Wunder, Ilias Efthimiopoulos, and Monika Koch-Müller
Eur. J. Mineral., 32, 469–482, https://doi.org/10.5194/ejm-32-469-2020, https://doi.org/10.5194/ejm-32-469-2020, 2020
Short summary
Short summary
The structural response of the NH4+ molecule to temperature and pressure changes is studied in ammonium phengite. The symmetry of the molecule is lowered by increasing P or decreasing T; the type and mechanism of this lowered symmetry is different in both cases. Devolatilisation (NH4+ and OH loss) of ammonium phengite is studied as well. This study confirms the wide stability range of phengite and its volatiles and thus has important implications for N and H recycling into the deep Earth.
Etienne Balan
Eur. J. Mineral., 32, 457–467, https://doi.org/10.5194/ejm-32-457-2020, https://doi.org/10.5194/ejm-32-457-2020, 2020
Short summary
Short summary
Corundum is an important oxide mineral which can contain low amounts of hydrogen-bearing structural defects. These defects are observed by infrared spectroscopy, but their atomic-scale geometry is still uncertain. Here, a theoretical approach makes it possible to relate most of the observed infrared bands to specific atomic configurations, highlighting the key role of other chemical impurities and defect clustering in the high-temperature incorporation of hydrogen in corundum.
Cited articles
Andreozzi, G. B., Bosi, F., and Longo, M.: Linking Mössbauer and
structural parameters in elbaite-schorl-dravite tourmalines, Am. Mineral.,
93, 658–666, https://doi.org/10.2138/am.2008.2721, 2008.
Balan, E.: Theoretical infrared spectra of OH defects in corundum (α-Al2O3), Eur. J. Miner., 32, 457–467,
https://doi.org/10.5194/ejm-32-457-2020, 2020.
Balan, E., Lazzeri, M., Delattre, S., Meheut, M., Refson, K., and Winkler,
B.: Anharmonicity of inner-OH stretching modes in hydrous phyllosilicates:
assessment from first-principles frozen- phonon calculations, Phys. Chem.
Miner., 34, 621–625, https://doi.org/10.1007/s00269-007-0176-4, 2007.
Baroni, S., de Gironcoli, S., Dal Corso, A., and Giannozzi, P.: Phonons and
related crystal properties from density-functional perturbation theory, Rev.
Mod. Phys., 73, 515–561, https://doi.org/10.1103/RevModPhys.73.515, 2001.
Berryman, E. J., Wunder, B., Ertl, A., Koch-Müller, M.,
Rhede, D., Scheidl, K, Giester, G., and Heinrich, W.: Influence of the
X-site composition on tourmaline's crystal structure: investigation of
synthetic K-dravite, dravite, oxy-uvite, and magnesio-foitite using SREF and
Raman spectroscopy, Phys. Chem. Miner., 43, 83–102,
https://doi.org/10.1007/s00269-015-0776-3, 2015.
Blanchard, M., Lazzeri, M., Mauri, F., and Balan, E.: First-principles
calculation of the infrared spectrum of hematite, Am. Mineral., 93,
1019–1027, https://doi.org/10.2138/am.2008.2813, 2008.
Bosi, F. and Lucchesi, S.: Crystal chemistry of the schorl-dravite series,
Eur. J. Mineral., 16, 335–344,
https://doi.org/10.1127/0935-1221/2004/0016-0335, 2004.
Bosi, F., Skogby, H., Agrosì, G., and Scandale, E.: Tsilaisite,
NaMn3Al6(Si6O18)(BO3)3 (OH)3OH, a new
mineral species of the tourmaline supergroup from Grotta d'Oggi, San Pietro
in Campo, island of Elba, Italy, Am. Mineral., 97, 989–994,
https://doi.org/10.2138/am.2012.4019, 2012.
Bosi, F., Andreozzi, G. B., Hålenius, H., and Skogby, H.: Experimental
evidence for partial Fe
Bosi, F., Skogby, H., and Balić-Žunić, T.: Thermal stability of
extended clusters in dravite: a combined EMP, SREF and FTIR study, Phys.
Chem. Mineral., 43, 395–407, https://doi.org/10.1007/s00269-016-0804-y, 2016.
Bosi, F., Pezzotta, F., Altieri, A., Andreozzi, G. B., Ballirano, P.,
Tempesta, G., Cempiìrek, J., Škoda, R., Filip, J., Čopjakovaì, R., Novák,
M., Kampf, A. R., Scribner, E. D., Groat, L. A. and Evans, R. J.: Celleriite,
□(Mn
Bosi, F., Pezzotta, F., Skogby, H., Altieri, A., Hålenius, U., Tempesta,
G., and Cempírek, J.: Princivalleite,
Na(Mn2Al)2Al6(Si6O18)(BO3)3(OH)3(OH),
a new mineral species of the tourmaline supergroup from Veddasca Valley,
Varese, Italy, Miner. Mag., 86, 78–86, https://doi.org/10.1180/mgm.2022.3, 2022b.
Bronzova, Y., Babushkina, M., Frank-Kamenetskaya, O., Vereshchagin, O.,
Rozhdestvenskaya, I., and Zolotarev, A.: Short-range order in Li–Al
tourmalines: IR spectroscopy, X-ray single crystal diffraction analysis and
a bond valence theory approach, Phys. Chem. Miner., 46, 815–825,
https://doi.org/10.1007/s00269-019-01042-0, 2019.
Castañeda, C., Oliveira, E. F., Gomes, N., and Soares, A. C. P.: Infrared
study of OH sites in tourmaline from the elbaite-schorl series, Am.
Mineral., 85, 1503–1507, https://doi.org/10.2138/am-2000-1021, 2000.
Cococcioni, M. and de Gironcoli, S.: Linear response approach to the
calculation of the effective interaction parameters in the LDA + U method,
Phys. Rev. B, 71, 035105, https://doi.org/10.1103/PhysRevB.71.035105, 2005.
Foit, F. F. and Rosenberg, P. E.: Coupled substitutions in the tourmaline
group, Contrib. Mineral. Petrol., 62, 109–127, 1977.
Foit Jr., F. F., Fuchs, Y., and Myers, P. E.: Chemistry of alkali-deficient
schorls from two tourmaline-dumortierite deposits, Am. Mineral., 74,
1317–1324, 1989.
Fuchs, Y., Lagache, M., Linares, J., Maury, R., and Varret, F.:
Mössbauer and optical spectrometry of selected
schörl–dravite tourmalines, Hyperfine Interactions, 96,
245–258, 1995.
Fuchs, Y., Lagache, M., and Linares, J.: Oxydation expérimentale de
Fe-tourmalines et corrélation avec une déprotonation des groupes
hydroxyle, C. R. Geosci., 334, 245–249,
https://doi.org/10.1016/S1631-0713(02)01755-8, 2002.
Fuchs, Y., Fourdrin, C., and Balan, E.: Theoretical OH stretching vibrations
in dravite, Eur. J. Mineral., 34, 239–251,
https://doi.org/10.5194/ejm-34-239-2022, 2022.
Gatta, G. D., Bosi, F., Mcintyre, G. J., and Skogby, H.: First accurate
location of two proton sites in tourmaline: A single-crystal neutron
diffraction study of oxy-dravite, Miner. Mag., 78, 681–692,
https://doi.org/10.1180/minmag.2014.078.3.15, 2014.
Giannozzi, P., Baroni, S., Bonini, N., Calandra, M., Car, R., Cavazzoni, C.,
Ceresoli, D., Chiarotti, G. L., Cococcioni, M., Dabo, I., Dal Corso, A., de
Gironcoli, S., Fabris, S., Fratesi, G., Gebauer, R., Gerstmann, U.,
Gougoussis, C., Kokalj, A., Lazzeri, M., Martin-Samos, L., Marzari, N.,
Mauri, F., Mazzarello, R., Paolini, S., Pasquarello, A., Paulatto, L.,
Sbraccia, C., Scandolo, S., Sclauzero, G., Seitsonen, A. P., Smogunov, A.,
Umari, P., and Wentzcovitch, R. M.: Quantum ESPRESSO: a modular and
open-source software project for quantum simulations of materials, J. Phys.
Cond. Mat., 21, 395502, https://doi.org/10.1088/0953-8984/21/39/395502,
2009 (code available at: http://www.quantum-espresso.org/, last access: 12 February 2023).
Gonzalez-CarrenÞo, T., Fernandez, M., and Sanz, J.: Infrared and electron
microprobe analysis of tourmalines, Phys. Chem. Miner., 15, 452–460,
https://doi.org/10.1007/BF00311124, 1988.
Hamann, D. R.: Optimized norm-conserving Vanderbilt pseudopotentials, Phys.
Rev. B, 88, 085117, https://doi.org/10.1103/PhysRevB.88.085117, 2013.
Hawthorne, F. C.: Short-range atomic arrangements in minerals, I: The
minerals of the amphibole, tourmaline and pyroxene supergroups, Eur. J.
Mineral., 28, 513–536, 2016.
Henry, D. J., Novák, M., Hawthorne, F. C., Ertl, A., Dutrow, B. L.,
Uher, P., and Pezzotta, F.: Nomenclature of the tourmaline-supergroup
minerals, Am. Mineral., 96, 895–913, https://doi.org/10.2138/am.2011.3636,
2011.
Hermansson, K.: Ab initio calculations of the fundamental OH frequency of
bound OH− ion, J. Chem. Phys., 95, 3578,
https://doi.org/10.1063/1.460808, 1991.
Hermansson, K.: Redshifts and blueshifts of OH vibrations, Int. J.
Quant. Chem., 45, 747–758, https://doi.org/10.1002/qua.560450621, 1993.
Hsu, H., Umemoto, K., Cococcioni, M., and Wentzcovitch, R.M.: The Hubbard U
correction for iron-bearing minerals: A discussion based on (Mg, Fe)SiO3
perovskite, Phys. Earth Pl. Int., 185, 13–19,
https://doi.org/10.1016/j.pepi.2010.12.001, 2011.
Kutzschbach, M., Wunder, B., Krstulovic, M., Ertl, A., Trumbull, R.,
Rocholl, A., and Giester, G.: First high-pressure synthesis of rossmanitic
tourmaline and evidence for the incorporation of Li at the X site, Phys.
Chem. Miner., 44, 353–363, 2017.
Libowitzky, E. and Beran, A.: The structure of hydrous species in nominally
anhydrous minerals: Information from polarized IR spectroscopy, Rev.
Mineral. Geochem., 62, 29–52, 2006.
Libowitzky, E. and Rossman, G. R.: An IR absorption calibration for water in
minerals, Am. Mineral., 82, 1111–1115, 1997.
Lin, J., Chen, N., Huang, D., and Pan, Y.: Iron pairs in beryl: New insights
from electron paramagnetic resonance, synchrotron X-ray absorption
spectroscopy, and ab initio calculations, Am. Mineral., 98, 1745–1753,
https://doi.org/10.2138/am.2013.4472, 2013.
Lensing-Burgdorf, M., Watenphul, A., Schlüter, J., and Mihailova, B.:
Crystal chemistry of tourmalines from the Erongo Mountains, Namibia, studied
by Raman spectroscopy, Eur. J. Mineral., 29, 257–267,
https://doi.org/10.1127/ejm/2017/0029-2607, 2017.
Momma, K. and Izumi, F.: VESTA 3 for three-dimensional visualization of
crystal, volumetric and morphology data, J. Appl. Crystallogr., 44,
1272–1276, https://doi.org/10.1107/S0021889811038970, 2011 (code available at: https://jp-minerals.org/vesta/en/, last access: 12 February 2023).
Nishio-Hamane, D., Minakawa, T., Yamaura, J., Oyama, T., Ohnishi, M., and
Shimobayashi, N.: Adachiite, a Si-poor member of the tourmaline supergroup
from the Kiura mine, Oita Prefecture, Japan, J. Mineral. Petrol. Sci., 109,
74–78, 2014.
Paulet, P. H., Fuchs, Y., Maury, R., Foit Jr., F. F., and Rosenberg, P. E.:
Zonalité des différents types de borosilicates dans les systèmes
hydrothermaux à or-argent de la Humboldt Range (Nevada, USA), C. R.
Acad. Sci., 313, 1155–1162, 1991.
Perdew, J. P., Burke, K., and Ernzerhof, M.: Generalized gradient
approximation made simple, Phys. Rev. Lett., 77, 3865–3868,
https://doi.org/10.1103/PhysRevLett.77.3865, 1996.
Pieczka, A. and Kraczka, J.: Oxidized tourmalines – a combined chemical, XRD
and Mössbauer study, Eur. J. Miner., 16, 309–321, 2004.
Prost, R.: The Influence of the Christiansen Effect on I.R. Spectra of
Powders, Clays Clay Miner., 21, 363–368,
https://doi.org/10.1346/CCMN.1973.0210512, 1973.
Schlipf, M. and Gygi, F.: Optimization algorithm for the generation of ONCV
pseudopotentials, Comput. Phys. Comm., 196, 36–44,
https://doi.org/10.1016/j.cpc.2015.05.011, 2015 (code available at: http://www.quantum-simulation.org/potentials/sg15_oncv/, last access: 12 February 2023).
Sherman, D. M.: Molecular orbital (SCF-Xα-SW) theory of metal-metal
charge transfer processes in minerals, Phys. Chem. Miner., 14, 364–367,
https://doi.org/10.1007/BF00309811, 1987.
Watenphul, A., Burgdorf, M., Schlüter, J., Horn, I., Malcherek, T., and
Mihailova, B.: Exploring the potential of Raman spectroscopy for
crystallochemical analyses of complex hydrous silicates: II. Tourmalines,
Am. Mineral., 101, 970–985, https://doi.org/10.2138/am-2016-5530, 2016.
Wilkins, R. W. T. and Ito, J.: Infrared spectra of some synthetic talcs, Am.
Mineral., 52, 1649–1661, 1967.
Wojdyr, M.: Fityk: a general-purpose peak fitting program, J. Appl.
Crystallogr., 43, 1126–1128, https://doi.org/10.1107/S0021889810030499,
2010 (code available at: https://fityk.nieto.pl/, last access:
12 February 2023).
Download
The requested paper has a corresponding corrigendum published. Please read the corrigendum first before downloading the article.
- Article
(3105 KB) - Full-text XML
- Corrigendum
-
Supplement
(254 KB) - BibTeX
- EndNote
Short summary
Assignment of OH-stretching bands to specific atomic-scale environments in tourmaline is still debated, which motivates detailed theoretical studies of their vibrational properties. We have theoretically investigated the OH-stretching spectrum of foitite, showing that specific OH bands observed in the vibrational spectra of iron-rich and Na-deficient tourmalines are affected by the magnetic configuration of iron ions and X-site vacancy ordering.
Assignment of OH-stretching bands to specific atomic-scale environments in tourmaline is still...
Special issue