Articles | Volume 35, issue 4
https://doi.org/10.5194/ejm-35-679-2023
© 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-35-679-2023
© Author(s) 2023. This work is distributed under
the Creative Commons Attribution 4.0 License.
the Creative Commons Attribution 4.0 License.
Research article
| 
24 Aug 2023
Research article |
| 24 Aug 2023
| 24 Aug 2023
OH incorporation and retention in eclogite-facies garnets from the Zermatt–Saas area (Switzerland) and their contribution to the deep water cycle
Institute of Earth Sciences, University of Lausanne, Géopolis building, UNIL-Mouline, 1015 Lausanne, Switzerland
Institute of Geological Sciences, University of Bern, Baltzerstrasse
3, 3012 Bern, Switzerland
Jörg Hermann
Institute of Geological Sciences, University of Bern, Baltzerstrasse
3, 3012 Bern, Switzerland
Pierre Lanari
Institute of Geological Sciences, University of Bern, Baltzerstrasse
3, 3012 Bern, Switzerland
Thomas Bovay
Institute of Earth Sciences, University of Lausanne, Géopolis building, UNIL-Mouline, 1015 Lausanne, Switzerland
Institute of Geological Sciences, University of Bern, Baltzerstrasse
3, 3012 Bern, Switzerland
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Kilian Lecacheur, Olivier Fabbri, Francesca Piccoli, Pierre Lanari, Philippe Goncalves, and Henri Leclère
Eur. J. Mineral., 36, 767–795, https://doi.org/10.5194/ejm-36-767-2024, https://doi.org/10.5194/ejm-36-767-2024, 2024
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In this study, we analyze a peculiar eclogite from the Western Alps, which not only recorded a classical subduction-to-exhumation path but revealed evidence of Ca-rich fluid–rock interaction. Chemical composition and modeling show that the rock experienced peak metamorphic conditions followed by Ca-rich pulsed fluid influx occurring consistently under high-pressure conditions. This research enhances our understanding of fluid–rock interactions in subduction settings.
Hugo Dominguez, Nicolas Riel, and Pierre Lanari
Geosci. Model Dev., 17, 6105–6122, https://doi.org/10.5194/gmd-17-6105-2024, https://doi.org/10.5194/gmd-17-6105-2024, 2024
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Predicting the behaviour of magmatic systems is important for understanding Earth's matter and heat transport. Numerical modelling is a technique that can predict complex systems at different scales of space and time by solving equations using various techniques. This study tests four algorithms to find the best way to transport the melt composition. The "weighted essentially non-oscillatory" algorithm emerges as the best choice, minimising errors and preserving system mass well.
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
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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.
Veronica Peverelli, Alfons Berger, Martin Wille, Thomas Pettke, Pierre Lanari, Igor Maria Villa, and Marco Herwegh
Solid Earth, 13, 1803–1821, https://doi.org/10.5194/se-13-1803-2022, https://doi.org/10.5194/se-13-1803-2022, 2022
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This work studies the interplay of epidote dissolution–precipitation and quartz dynamic recrystallization during viscous granular flow in a deforming epidote–quartz vein. Pb and Sr isotope data indicate that epidote dissolution–precipitation is mediated by internal/recycled fluids with an additional external fluid component. Microstructures and geochemical data show that the epidote material is redistributed and chemically homogenized within the deforming vein via a dynamic granular fluid pump.
Veronica Peverelli, Tanya Ewing, Daniela Rubatto, Martin Wille, Alfons Berger, Igor Maria Villa, Pierre Lanari, Thomas Pettke, and Marco Herwegh
Geochronology, 3, 123–147, https://doi.org/10.5194/gchron-3-123-2021, https://doi.org/10.5194/gchron-3-123-2021, 2021
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This work presents LA-ICP-MS U–Pb geochronology of epidote in hydrothermal veins. The challenges of epidote dating are addressed, and a protocol is proposed allowing us to obtain epidote U–Pb ages with a precision as good as 5 % in addition to the initial Pb isotopic composition of the epidote-forming fluid. Epidote demonstrates its potential to be used as a U–Pb geochronometer and as a fluid tracer, allowing us to reconstruct the timing of hydrothermal activity and the origin of the fluid(s).
Michael C. Jollands, Hugh St.C. O'Neill, Andrew J. Berry, Charles Le Losq, Camille Rivard, and Jörg Hermann
Eur. J. Mineral., 33, 113–138, https://doi.org/10.5194/ejm-33-113-2021, https://doi.org/10.5194/ejm-33-113-2021, 2021
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How, and how fast, does hydrogen move through crystals? We consider this question by adding hydrogen, by diffusion, to synthetic crystals of olivine doped with trace amounts of chromium. Even in a highly simplified system, the behaviour of hydrogen is complex. Hydrogen can move into and through the crystal using various pathways (different defects within the crystal) and hop between these pathways too.
Felix Hentschel, Emilie Janots, Claudia A. Trepmann, Valerie Magnin, and Pierre Lanari
Eur. J. Mineral., 32, 521–544, https://doi.org/10.5194/ejm-32-521-2020, https://doi.org/10.5194/ejm-32-521-2020, 2020
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We analysed apatite–allanite/epidote coronae around monazite and xenotime in deformed Permian pegmatites from the Austroalpine basement. Microscopy, chemical analysis and EBSD showed that these coronae formed by dissolution–precipitation processes during deformation of the host rocks. Dating of monazite and xenotime confirmed the magmatic origin of the corona cores, while LA-ICP-MS dating of allanite established a date of ~ 60 Ma for corona formation and deformation in the Austroalpine basement.
Alice Vho, Pierre Lanari, Daniela Rubatto, and Jörg Hermann
Solid Earth, 11, 307–328, https://doi.org/10.5194/se-11-307-2020, https://doi.org/10.5194/se-11-307-2020, 2020
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This study presents an approach that combines equilibrium thermodynamic modelling with oxygen isotope fractionation modelling for investigating fluid–rock interaction in metamorphic systems. An application to subduction zones shows that chemical and isotopic zoning in minerals can be used to determine feasible fluid sources and the conditions of interaction. Slab-derived fluids can cause oxygen isotope variations in the mantle wedge that may result in anomalous isotopic signatures of arc lavas.
Laura Stutenbecker, Peter M. E. Tollan, Andrea Madella, and Pierre Lanari
Solid Earth, 10, 1581–1595, https://doi.org/10.5194/se-10-1581-2019, https://doi.org/10.5194/se-10-1581-2019, 2019
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The Aar and Mont Blanc regions in the Alps are large granitoid massifs characterized by high topography. We analyse when these granitoids were first exhumed to the surface. We test this by tracking specific garnet grains, which are exclusively found in the granitoid massifs, in the sediments contained in the alpine foreland basin. This research ties in with ongoing debates on the timing and mechanisms of mountain building.
Francesco Giuntoli, Pierre Lanari, and Martin Engi
Solid Earth, 9, 167–189, https://doi.org/10.5194/se-9-167-2018, https://doi.org/10.5194/se-9-167-2018, 2018
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Continental high-pressure terranes in orogens offer insight into deep recycling and transformation processes that occur in subduction zones. These remain poorly understood, and currently debated ideas need testing. We document complex garnet zoning in eclogitic mica schists from the Sesia Zone (western Italian Alps). These retain evidence of two orogenic cycles and provide detailed insight into resorption, growth, and diffusion processes induced by fluid pulses under high-pressure conditions.
Francesco Giuntoli, Pierre Lanari, Marco Burn, Barbara Eva Kunz, and Martin Engi
Solid Earth, 9, 191–222, https://doi.org/10.5194/se-9-191-2018, https://doi.org/10.5194/se-9-191-2018, 2018
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Subducted continental terranes commonly comprise an assembly of subunits that reflect the different tectono-metamorphic histories they experienced in the subduction zone. Our challenge is to unravel how, when, and in which part of the subduction zone these subunits were juxtaposed. Our study documents when and in what conditions re-equilibration took place. Results constrain the main stages of mineral growth and deformation, associated with fluid influx that occurred in the subduction channel.
Related subject area
Spectroscopic methods applied to minerals
Laser-induced breakdown spectroscopy analysis of tourmaline: protocols, procedures, and predicaments
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
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
Effect of Fe–Fe interactions and X-site vacancy ordering on the OH-stretching spectrum of foitite
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)
Nancy J. McMillan and Barbara L. Dutrow
Eur. J. Mineral., 36, 369–379, https://doi.org/10.5194/ejm-36-369-2024, https://doi.org/10.5194/ejm-36-369-2024, 2024
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The mineral tourmaline records the geologic environment in which it crystallizes. Methods were developed for laser-induced breakdown spectroscopy analysis of tourmaline. Problems that were solved include the spacing between analysis locations to avoid the recast layer from previous analyses, the efficacy of using cleaning shots prior to data acquisition, the number of analyses needed to obtain a representative average analysis, and the effect of spectrometer drift on multivariate analysis.
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
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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
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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.
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
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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.
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
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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
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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, Guillaume Radtke, Chloé Fourdrin, Lorenzo Paulatto, Heinrich A. Horn, and Yves Fuchs
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.
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
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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
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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 %.
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
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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
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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
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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.
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
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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
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
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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.
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
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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
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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.
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
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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
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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.
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
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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
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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
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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
Agard, P., Monié, P., Jolivet, L., and Goffé, B.: Exhumation of the
Schistes Lustrés complex: in situ laser probe 40Ar
Aines, R. D. and Rossman, G. R.: The hydrous component in garnets:
pyralspites, Am. Mineral., 69, 1116–1126, 1984.
Amato, J. M., Johnson, C. M., Baumgartner, L. P., and Beard, B. L.: Rapid
exhumation of the Zermatt-Saas ophiolite deduced from high-precision SmNd
and RbSr geochronology, Earth Planet. Sc. Lett., 171, 425–438,
https://doi.org/10.1016/S0012-821X(99)00161-2, 1999.
Amthauer, G. and Rossman, G. R.: The hydrous component in andradite garnet,
Am. Mineral., 83, 835–840, https://doi.org/10.2138/am-1998-7-815, 1998.
Andrut, M., Wildner, M., and Beran, A.: The crystal chemistry of
birefringent natural uvarovites, Part IV. OH defect incorporation mechanisms
in non-cubic garnets derived from polarized IR spectroscopy, Eur. J.
Mineral., 14, 1019–1026, https://doi.org/10.1127/0935-1221/2002/0014-1019,
2002.
Angiboust, S., Agard, P., Jolivet, L., and Beyssac, O.: The Zermatt-Saas
ophiolite: the largest (60-km wide) and deepest (c. 70–80 km) continuous
slice of oceanic lithosphere detached from a subduction zone?, Terra Nova,
21, 171–180, https://doi.org/10.1111/j.1365-3121.2009.00870.x, 2009.
Armbruster, T., Birrer, J., Libowitzky, E., and Beran, A.: Crystal chemistry
of Ti-bearing andradites, Eur. J. Mineral., 10, 907–922,
https://doi.org/10.1127/ejm/10/5/0907, 1998.
Arredondo, E. H., Rossman, G. R., and Lumpkin, G. R.: Hydrogen in
spessartine-almandine garnets as a tracer of granitic pegmatite evolution,
Am. Mineral., 86, 485–490, https://doi.org/10.2138/am-2001-0412, 2001.
Basso, R., Cimmino, F., and Messiga, B.: Crystal-chemistry of hydrogarnets
from 3 different microstructural sites of a basaltic metarodingite from the
Voltri-massif (Western Liguria, Italy), Neues Jahrb. Mineral.-Abh., 148,
246–258, 1984.
Baxter, E. F. and Caddick, M. J.: Garnet growth as a proxy for progressive
subduction zone dehydration, Geology, 41, 643–646,
https://doi.org/10.1130/G34004.1, 2013.
Bearth, P.: Die Ophiolithe der Zone von Zermatt-Saas Fee, Kümmerly and Frey, Bern, 1967.
Bell, D. R., Ihinger, P. D., and Rossman, G. R.: Quantitative analysis of
trace OH in garnet and pyroxenes, Am. Mineral., 80, 465–474,
https://doi.org/10.2138/am-1995-5-607, 1995.
Blanchard, M. and Ingrin, J.: Hydrogen diffusion in Dora Maira pyrope, Phys.
Chem. Miner., 31, 593–605, https://doi.org/10.1007/s00269-004-0421-z,
2004a.
Blanchard, M. and Ingrin, J.: Kinetics of deuteration in pyrope, Eur. J.
Mineral., 16, 567–576, https://doi.org/10.1127/0935-1221/2004/0016-0567,
2004b.
Bovay, T., Rubatto, D., and Lanari, P.: Pervasive fluid-rock interaction in
subducted oceanic crust revealed by oxygen isotope zoning in garnet,
Contrib. Mineral. Petrol., 176, 55,
https://doi.org/10.1007/s00410-021-01806-4, 2021.
Bovay, T., Lanari, P., Rubatto, D., Smit, M., and Piccoli, F.:
Pressure–temperature–time evolution of subducted crust revealed by complex
garnet zoning (Theodul Glacier Unit, Switzerland), J. Metamorph. Geol., 40,
175–206, https://doi.org/10.1111/jmg.12623, 2022.
Bowtell, S. A., Cliff, R. A., and Barnicoat, A. C.: Sm-Nd isotopic evidence
on the age of eclogitization in the Zermatt-Saas ophiolite, J. Metamorph.
Geol., 12, 187–196, https://doi.org/10.1111/j.1525-1314.1994.tb00013.x,
1994.
Bucher, K., Fazis, Y., De Capitani, C., and Grapes, R.: Blueschists,
eclogites, and decompression assemblages of the Zermatt-Saas ophiolite:
High-pressure metamorphism of subducted Tethys lithosphere, Am. Mineral.,
90, 821–835, 2005.
Bucher, K., Weisenberger, T. B., Klemm, O., and Weber, S.: Decoding the
complex internal chemical structure of garnet porphyroblasts from the
Zermatt area, Western Alps, J. Metamorph. Geol., 37, 1151–1169,
https://doi.org/10.1111/jmg.12506, 2019.
Chen, R.-X., Zheng, Y.-F., Gong, B., Zhao, Z.-F., Gao, T.-S., Chen, B., and
Wu, Y.-B.: Origin of retrograde fluid in ultrahigh-pressure metamorphic
rocks: Constraints from mineral hydrogen isotope and water content changes
in eclogite–gneiss transitions in the Sulu orogen, Geochim. Cosmochim.
Ac., 71, 2299–2325, https://doi.org/10.1016/j.gca.2007.02.012, 2007.
Chinner, G. A. and Dixon, J. E.: Some High-pressure Parageneses of the
Allalin Gabbro, Valais, Switzerland, J. Petrol., 14, 185–202,
https://doi.org/10.1093/petrology/14.2.185, 1973.
Cho, H. and Rossman, G. R.: Single-crystal NMR studies of low-concentration
hydrous species in minerals: Grossular garnet, Am. Mineral., 78, 1149–1164,
1993.
Cohen-Addad, C., Ducros, P., and Bertaut, E. F.: Etude de la Substitution du
groupement SiO4 par (OH)4 dans les composés Al2Ca3(OH)12 et
Al2Ca3(SiO4)2.16(OH)3.36 de type grenat, Acta Crystallogr., 23, 220–230,
1967.
Crank, J.: The Mathematics of diffusion, Clarendon–Oxford university press, ISBN: 0 19 853344 6, 1975.
Foreman, D. W.: Neutron and X-Ray Diffraction Study of Ca3Al2(O4D4)3, a
Garnetoid, J. Chem. Phys., 48, 3037–3041,
https://doi.org/10.1063/1.1669569, 1968.
Freeze, R. A. and Cherry, J. A.: Groundwater, Prentice-Hall, Englewood
Cliffs, N.J. 07632, ISBN: 0-13-365312-9, 604 pp., 1979.
Geiger, C. A. and Rossman, G. R.: Micro- and nano-size hydrogarnet clusters
and proton ordering in calcium silicate garnet: Part I. The quest to
understand the nature of “water” in garnet continues, Am. Mineral., 105,
455–467, https://doi.org/10.2138/am-2020-7256, 2020a.
Geiger, C. A. and Rossman, G. R.: Micro- and nano-size hydrogarnet clusters
in calcium silicate garnet: Part II. Mineralogical, petrological, and
geochemical aspects, Am. Mineral., 105, 468–478,
https://doi.org/10.2138/am-2020-7257, 2020b.
Geiger, C. A., Langer, K., Bell, D. R., Rossman, G. R., and Winkler, B.: The
hydroxide component in synthetic pyrope, Am. Mineral., 76, 49–59, 1991.
Gose, J. and Schmädicke, E.: Water Incorporation in Garnet: Coesite
versus Quartz Eclogite from Erzgebirge and Fichtelgebirge, J. Petrol., 59,
207–232, https://doi.org/10.1093/petrology/egy022, 2018.
Gou, Y., Wang, Q., Li, Y., and Wirth, R.: Water Content in Garnet from
Eclogites: Implications for Water Cycle in Subduction Channels, Minerals,
10, 410, https://doi.org/10.3390/min10050410, 2020.
Handy, M. R., M. Schmid, S., Bousquet, R., Kissling, E., and Bernoulli, D.:
Reconciling plate-tectonic reconstructions of Alpine Tethys with the
geological–geophysical record of spreading and subduction in the Alps,
Earth-Sci. Rev., 102, 121–158,
https://doi.org/10.1016/j.earscirev.2010.06.002, 2010.
Katayama, I., Nakashima, S., and Yurimoto, H.: Water content in natural
eclogite and implication for water transport into the deep upper mantle,
Lithos, 86, 245–259, 2006.
Kempf, E. D., Hermann, J., Reusser, E., Baumgartner, L. P., and Lanari, P.:
The role of the antigorite + brucite to olivine reaction in subducted
serpentinites (Zermatt, Switzerland), Swiss J. Geosci., 113, 16,
https://doi.org/10.1186/s00015-020-00368-0, 2020.
Khomenko, V. M., Langer, K., Beran, A., Koch-Müller, M., and Fehr, T.:
Titanium substitution and OH-bearing defects in hydrothermally grown pyrope
crystals, Phys. Chem. Miner., 20, 483–488,
https://doi.org/10.1007/BF00203218, 1994.
Kühberger, A., Fehr, T., Huckenholz, H. G., and Amthauer, G.: Crystal
chemistry of a natural schorlomite and Ti-andradites synthesized at
different oxygen fugacities, Phys. Chem. Miner., 16, 734–740,
https://doi.org/10.1007/BF00209694, 1989.
Kurka, A.: Hydrogen in Ca-rich garnets: diffusion and stability of
OH-defects, PhD thesis, Toulouse III Paul Sabatier, Toulouse, France, 371 pp., 2005.
Kurka, A., Blanchard, M., and Ingrin, J.: Kinetics of hydrogen extraction
and deuteration in grossular, Mineral. Mag., 69, 359–371,
https://doi.org/10.1180/0026461056930257, 2005.
Lager, G. A., Armbruster, T., and Faber, J.: Neutron and X-ray diffraction
study of hydrogarnet Ca3Al2(O4H4)3, Am. Mineral., 72, 756–765, 1987.
Lanari, P., Vidal, O., De Andrade, V., Dubacq, B., Lewin, E., Grosch, E. G.,
and Schwartz, S.: XMapTools: A MATLAB© – based program for electron
microprobe X-ray image processing and geothermobarometry, Comput. Geosci.,
62, 227–240, https://doi.org/10.1016/j.cageo.2013.08.010, 2014.
Lanari, P., Giuntoli, F., Loury, C., Burn, M., and Engi, M.: An inverse
modeling approach to obtain P–T conditions of metamorphic stages involving
garnet growth and resorption, Eur. J. Mineral., 29, 181–199,
https://doi.org/10.1127/ejm/2017/0029-2597, 2017.
Lanari, P., Vho, A., Bovay, T., Airaghi, L., and Centrella, S.: Quantitative
compositional mapping of mineral phases by electron probe micro-analyser,
in: Metamorphic Geology: Microscale to Mountain Belts, Vol. 478, edited by:
Ferrero, S., Lanari, P., Goncalves, P., and Grosch, E. G., Geological Society of London, Special Publications, https://doi.org/10.1144/SP478.4, 2019.
Lemoine, M., Bas, T., Arnaud-Vanneau, A., Arnaud, H., Dumont, T., Gidon, M.,
Bourbon, M., de Graciansky, P.-C., Rudkiewicz, J.-L., Megard-Galli, J., and
Tricart, P.: The continental margin of the Mesozoic Tethys in the Western
Alps, Mar. Pet. Geol., 3, 179–199,
https://doi.org/10.1016/0264-8172(86)90044-9, 1986.
Li, X.-P., Rahn, M., and Bucher, K.: Serpentinites of the Zermatt-Saas
ophiolite complex and their texture evolution, J. Metamorph. Geol., 22,
159–177, https://doi.org/10.1111/j.1525-1314.2004.00503.x, 2004.
Lu, R. and Keppler, H.: Water solubility in pyrope to 100 kbar, Contrib.
Mineral. Petrol., 129, 35–42, https://doi.org/10.1007/s004100050321, 1997.
Luoni, P., Rebay, G., Spalla, M. I., and Zanoni, D.: UHP Ti-chondrodite in
the Zermatt-Saas serpentinite: Constraints on a new tectonic scenario, Am.
Mineral., 103, 1002–1005, https://doi.org/10.2138/am-2018-6460, 2018.
Maldener, J., Hösch, A., Langer, K., and Rauch, F.: Hydrogen in some
natural garnets studied by nuclear reaction analysis and vibrational
spectroscopy, Phys. Chem. Miner., 30, 337–344,
https://doi.org/10.1007/s00269-003-0321-7, 2003.
Martin, S., Rebay, G., Kienast, J.-R., and Mével, C.: An eclogitised
oceanic palaeo-hydrothermal field from the St. Marcel Valley (Italian
Western Alps), Ofioliti, 33, 49–63,
2008.
Mosenfelder, J. L., von der Handt, A., Withers, A. C., Bureau, H., Raepsaet,
C., and Rossman, G. R.: Coupled hydrogen and fluorine incorporation in
garnet: New constraints from FTIR, ERDA, SIMS, and EPMA, Am. Mineral., 107,
587–602, https://doi.org/10.2138/am-2021-7880, 2022.
Nace, R. L.: Scientific framework of world water balance, United Nations Educational, Scientific and Cultural Organization, SC.70/XXI.7/A, https://unesdoc.unesco.org/ark:/48223/pf0000073095 (last access: 10 July 2023), 1971.
Okamoto, K. L.: Petrological study of the diamond grade eclogite in the
Kokchetav massif, northern Kazakhstan, Isl. Arc, 9, 379–399, 2000.
Peacock, S. M.: Fluid Processes in subduction Zones, Science, 248, 329–337,
https://doi.org/10.1126/science.248.4953.329, 1990.
Rebay, G., Zanoni, D., Langone, A., Luoni, P., Tiepolo, M., and Spalla, M.
I.: Dating of ultramafic rocks from the Western Alps ophiolites discloses
Late Cretaceous subduction ages in the Zermatt-Saas Zone, Geol. Mag., 155,
298–315, https://doi.org/10.1017/S0016756817000334, 2018.
Reinecke, T.: Very-high-pressure metamorphism and uplift of coesite-bearing
metasediments from the Zermatt-Saas zone, Western Alps, Eur. J. Mineral., 3,
7–18, https://doi.org/10.1127/ejm/3/1/0007, 1991.
Reynes, J., Jollands, M., Hermann, J., and Ireland, T.: Experimental
constraints on hydrogen diffusion in garnet, Contrib. Mineral. Petrol., 173,
69, https://doi.org/10.1007/s00410-018-1492-z, 2018.
Reynes, J., Lanari, P., and Hermann, J.: A mapping approach for the
investigation of Ti–OH relationships in metamorphic garnet, Contrib.
Mineral. Petrol., 175, 46, https://doi.org/10.1007/s00410-020-01681-5, 2020.
Rossman, G. R. and Aines, R. D.: The hydrous components in garnets:
Grossular-hydrogrossular, Am. Mineral., 76, 1153–1164, 1991.
Rossman, G. R., Beran, A., and Langer, K.: The hydrous component of pyrope
from the Dora Maira Massif, Western Alps, Eur. J. Mineral., 1, 151–154,
https://doi.org/10.1127/ejm/01/1/0151, 1989.
Rubatto, D., Gebauer, D., and Fanning, M.: Jurassic formation and Eocene
subduction of the Zermatt–Saas-Fee ophiolites: implications for the
geodynamic evolution of the Central and Western Alps, Contrib. Mineral.
Petrol., 132, 269–287, https://doi.org/10.1007/s004100050421, 1998.
Rüpke, L. H., Morgan, J. P., Hort, M., and Connolly, J. A. D.:
Serpentine and the subduction zone water cycle, Earth Planet. Sc. Lett.,
223, 17–34, https://doi.org/10.1016/j.epsl.2004.04.018, 2004.
Schmädicke, E. and Gose, J.: Water transport by subduction: Clues from
garnet of Erzgebirge UHP eclogite, Am. Mineral., 102, 975–986,
https://doi.org/10.2138/am-2017-5920, 2017.
Schmädicke, E. and Gose, J.: Water in garnet of garnetite
(metarodingite) and eclogite from the Erzgebirge and the Lepontine Alps, J.
Metamorph. Geol., 38, 905–933, https://doi.org/10.1111/jmg.12554, 2020.
Schmidt, M. W. and Poli, S.: Experimentally based water budgets for
dehydrating slabs and consequences for arc magma generation, Earth Planet.
Sc. Lett., 163, 361–379, https://doi.org/10.1016/S0012-821X(98)00142-3,
1998.
Schwandt, C. S., Cygan, R. T., and Westrich, H. R.: Mg self-diffusion in
pyrope garnet, Am. Mineral., 80, 483–490,
https://doi.org/10.2138/am-1995-5-609, 1995.
Sheng, Y.-M., Xia, Q.-K., Dallai, L., Yang, X.-Z., and Hao, Y.-T.: H2O
contents and D
Vho, A., Lanari, P., Rubatto, D., and Hermann, J.: Tracing fluid transfers in subduction zones: an integrated thermodynamic and δ18O fractionation modelling approach, Solid Earth, 11, 307–328, https://doi.org/10.5194/se-11-307-2020, 2020.
Xia, Q.-K., Sheng, Y.-M., Yang, X.-Z., and Yu, H.-M.: Heterogeneity of water
in garnets from UHP eclogites, eastern Dabieshan, China, Chem. Geol., 224,
237–246, https://doi.org/10.1016/j.chemgeo.2005.08.003, 2005.
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.
Garnet is a high-pressure mineral that may incorporate very small amounts of water in its...
