Articles | Volume 34, issue 6
https://doi.org/10.5194/ejm-34-627-2022
© Author(s) 2022. 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-34-627-2022
© Author(s) 2022. This work is distributed under
the Creative Commons Attribution 4.0 License.
the Creative Commons Attribution 4.0 License.
Research article
| 
14 Dec 2022
Research article |
| 14 Dec 2022
| 14 Dec 2022
Molecular overtones and two-phonon combination bands in the near-infrared spectra of talc, brucite and lizardite
Etienne Balan
CORRESPONDING AUTHOR
Sorbonne Université, CNRS, MNHN, IRD, Institut de Minéralogie,
de Physique des Matériaux et de Cosmochimie (IMPMC), 4 place Jussieu,
75252 Paris CEDEX 05, France
Lorenzo Paulatto
Sorbonne Université, CNRS, MNHN, IRD, Institut de Minéralogie,
de Physique des Matériaux et de Cosmochimie (IMPMC), 4 place Jussieu,
75252 Paris CEDEX 05, France
Qianyu Deng
Sorbonne Université, CNRS, MNHN, IRD, Institut de Minéralogie,
de Physique des Matériaux et de Cosmochimie (IMPMC), 4 place Jussieu,
75252 Paris CEDEX 05, France
Keevin Béneut
Sorbonne Université, CNRS, MNHN, IRD, Institut de Minéralogie,
de Physique des Matériaux et de Cosmochimie (IMPMC), 4 place Jussieu,
75252 Paris CEDEX 05, France
Maxime Guillaumet
Sorbonne Université, CNRS, MNHN, IRD, Institut de Minéralogie,
de Physique des Matériaux et de Cosmochimie (IMPMC), 4 place Jussieu,
75252 Paris CEDEX 05, France
Benoît Baptiste
Sorbonne Université, CNRS, MNHN, IRD, Institut de Minéralogie,
de Physique des Matériaux et de Cosmochimie (IMPMC), 4 place Jussieu,
75252 Paris CEDEX 05, France
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Michael C. Jollands, Shiyun Jin, Martial Curti, Maxime Guillaumet, Keevin Béneut, Paola Giura, and Etienne Balan
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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
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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.
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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.
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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.
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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
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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
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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
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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
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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.
Quentin Bollaert, Mathieu Chassé, Guillaume Morin, Benoît Baptiste, Alexandra Courtin, Laurence Galoisy, Gautier Landrot, Cécile Quantin, and Georges Calas
Eur. J. Mineral., 36, 55–72, https://doi.org/10.5194/ejm-36-55-2024, https://doi.org/10.5194/ejm-36-55-2024, 2024
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X-ray absorption spectroscopy (XAS) was successfully used to investigate the atomic-scale environment of niobium (Nb) in ore minerals and Nb-doped compounds of technological importance. The demonstrated sensitivity of this technique to Nb minerals could help decipher Nb speciation in mining contexts such as hydrothermal and lateritic deposits and rationalize the origin of the enhanced physico-chemical properties of Nb-doped materials.
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
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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.
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Minerals in a vein network from the Aravis limestone (Haute-Savoie, France) include carbonates, quartz, fluorite and phyllosilicates, crystallized at around 7 km depth and 190 °C. The mineralogy has been studied with emphasis on the chlorite types: chamosite (iron-rich), cookeite (lithium-rich) and sudoite. The presence of the three chlorite types sheds light on their phase diagrams, and observed cationic substitutions confirm the need for more systematic measurement of lithium in chlorite.
Karina P. P. Marques, Thierry Allard, Cécile Gautheron, Benoît Baptiste, Rosella Pinna-Jamme, Guillaume Morin, Ludovic Delbes, and Pablo Vidal-Torrado
Eur. J. Mineral., 35, 383–395, https://doi.org/10.5194/ejm-35-383-2023, https://doi.org/10.5194/ejm-35-383-2023, 2023
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We proposed a new non-destructive mineralogical methodology on sub-millimeter grains that allows us to quantify the hematite and goethite content and hematite / goethite ratio of grains prior to (U–Th) / He geochronological analysis. (U–Th) / He data performed on different aliquots with different acquisition times show no remarkable differences in age, opening a new way to investigate the (U–Th) / He data evolution in supergene lateritic duricrusts.
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Eur. J. Mineral., 35, 105–116, https://doi.org/10.5194/ejm-35-105-2023, https://doi.org/10.5194/ejm-35-105-2023, 2023
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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.
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
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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.
Karina Patricia Prazeres Marques, Thierry Allard, Cécile Gautheron, Benoît Baptiste, Rosella Pinna-Jamme, Guillaume Morin, Ludovic Delbes, and Pablo Vidal-Torrado
Geochronology Discuss., https://doi.org/10.5194/gchron-2022-9, https://doi.org/10.5194/gchron-2022-9, 2022
Preprint withdrawn
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We proposed a new non-destructive mineralogical methodology on inframilimetric grains that allows to quantify the hematite and goethite content and hematite/goethite ratio of grains prior to (U-Th)/He geochronological analysis. (U-Th)/He data performed on different aliquots with different acquisition time shows no remarkable differences in age, opening a new way to investigate the (U-Th)/He data evolution in supergene lateritic duricrusts.
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.
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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.
The near-infrared spectra of hydrous minerals involve OH stretching vibrations, but their...
