Articles | Volume 33, issue 4
https://doi.org/10.5194/ejm-33-425-2021
© Author(s) 2021. 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-33-425-2021
© Author(s) 2021. This work is distributed under
the Creative Commons Attribution 4.0 License.
the Creative Commons Attribution 4.0 License.
Research article
| 
30 Jul 2021
Research article |
| 30 Jul 2021
| 30 Jul 2021
The intracrystalline microstructure of Monte Fico lizardite, by optics, μ-Raman spectroscopy and TEM
Giancarlo Capitani
Department of Earth and Environmental Sciences (DISAT), University of
Milano-Bicocca, Milan, 20126, Italy
Roberto Compagnoni
Department of Earth Sciences, University of Turin, Turin, 10125, Italy
“Giovanni Scansetti” Interdepartmental Centre for Studies on Asbestos
and Other Toxic Particulates, University of Turin, Turin, 10125 Italy
Department of Earth Sciences, University of Turin, Turin, 10125, Italy
“Giovanni Scansetti” Interdepartmental Centre for Studies on Asbestos
and Other Toxic Particulates, University of Turin, Turin, 10125 Italy
Serena Botta
Department of Earth Sciences, University of Turin, Turin, 10125, Italy
“Giovanni Scansetti” Interdepartmental Centre for Studies on Asbestos
and Other Toxic Particulates, University of Turin, Turin, 10125 Italy
Marcello Mellini
“Giovanni Scansetti” Interdepartmental Centre for Studies on Asbestos
and Other Toxic Particulates, University of Turin, Turin, 10125 Italy
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Luca Barale, Giancarlo Capitani, Paolo Castello, Roberto Compagnoni, Roberto Cossio, Gianluca Fiore, Linda Pastero, and Marcello Mellini
Eur. J. Mineral., 35, 347–360, https://doi.org/10.5194/ejm-35-347-2023, https://doi.org/10.5194/ejm-35-347-2023, 2023
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The first occurrence of centimeter-thick PS-15 polygonal serpentine veins from ultramafics of Monte Avic, Val d'Aosta, is here reported. The combined mineralogical study led by three techniques with different resolutions has provided new analytical tools capable of recognizing the PS-15 polygonal serpentine. In particular, X-ray powder diffraction data (XRPD) and micro-Raman recognize polygonal serpentine more quickly and easily than transmission electron microscopy (TEM) but equally rigorously.
Jane A. Gilotti, William C. McClelland, Simon Schorn, Roberto Compagnoni, and Matthew A. Coble
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We show that metamorphosed sedimentary rocks in the Western Alps have a detrital zircon signature that connects them to the Adrian plate along the Gondwana margin. We used zircon to learn that a jadeite-bearing orthogneiss intruded into these strata in the Ordovician (at ~460 Ma) and was metamorphosed at high pressure during early Alpine subduction of Adria beneath Europe at ~78 Ma. Our results are consistent with the complex subduction of Adria before full-on collision with the European plate.
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Eur. J. Mineral., 35, 347–360, https://doi.org/10.5194/ejm-35-347-2023, https://doi.org/10.5194/ejm-35-347-2023, 2023
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The first occurrence of centimeter-thick PS-15 polygonal serpentine veins from ultramafics of Monte Avic, Val d'Aosta, is here reported. The combined mineralogical study led by three techniques with different resolutions has provided new analytical tools capable of recognizing the PS-15 polygonal serpentine. In particular, X-ray powder diffraction data (XRPD) and micro-Raman recognize polygonal serpentine more quickly and easily than transmission electron microscopy (TEM) but equally rigorously.
Roberto Giustetto, Stefania Padovan, Luca Barale, and Roberto Compagnoni
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The Neolithic polished stone industry of Chiomonte was studied with a multi-analytical approach, with the aim of providing information about the raw material origins and supply sources. Most tools are made of greenstones. Specific mineral and chemical markers were found, pointing to an origin in the Monviso area. The presence on roughouts and broken tools with raw surfaces ascribable to pebbles or cobbles suggests that these rocks had been picked up from glacial or alluvial secondary sources.
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Etienne Balan
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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
Amiguet, E., Reynard, B., Caracas, R., Van de Moortele, B., and Wang, Y.:
Creep of phyllosilicates at the onset of plate tectonics, Earth
Planet. Sc. Lett., 345, 142–150, 2012.
Auzende, A. L., Daniel, I., Reynard, B., Lemaire, C., and Guyot, F.:
High-pressure behaviour of serpentine minerals: A Raman spectroscopic study,
Phys. Chem. Miner., 31, 269–277, 2004.
Compagnoni, R., Cossio, R., and Mellini, M.: Raman anisotropy in serpentine
minerals, with a caveat on identification, J. Raman Spectr., 52, 1334–1345,
https://doi.org/10.1002/jrs.6128, 2021.
Fuchs, Y., Linares, J., and Mellini, M.: Mössbauer and infrared
spectrometry of lizardite-1T from Monte Fico, Elba. Phys. Chem. Miner., 26,
111–115, 1998.
Gailhanou, H., Blanc, P., Mikaelian, G., Rogez, J., and Kawaji, H.:
Thermodynamic properties of lizardite, determined by calorimetry.
International Symposium on Solubility Phenomena and Related Equilibrium
Processes (ISSP), Tours, France, HAL Id: hal-01720566, available at:
https://hal-brgm.archives-ouvertes.fr/hal-01720566 (last access: 26 July 2021), 2018.
Gregorkiewitz, M., Lebech, B., Mellini, M., and Viti, C.: Hydrogen positions
and thermal expansion in lizardite-1T from Elba: a low-temperature study
using Rietveld refinement of neutron diffraction data, Am.
Mineral., 81, 1111–1116, 1996.
Hilairet, N., Daniel, I., and Reynard, B.: P–V Equations of State and the
relative stabilities of serpentine varieties, Phys. Chem Miner., 33,
629–637, 2006.
Hirose, T., Bystricky, M., Kunze, K., and Stünitz, H.: Semi-brittle flow
during dehydration of lizardite–chrysotile serpentinite deformed in
torsion: Implications for the rheology of oceanic lithosphere, Earth
Planet. Sc. Lett., 249, 484–493, 2006.
Lacinska, A. M., Styles, M. T., Bateman, K., Wagner, D., Hall, M. R., Gowing,
C., and Brown, P. D.: Acid-dissolution of antigorite, chrysotile and
lizardite for ex situ carbon capture and storage by mineralisation, Chem.
Geol., 437, 153–169, 2016.
Mellini, M. and Viti, C.: Crystal structure of lizardite-1T from Elba, Italy,
Am. Mineral., 79, 1194–1198, 1994.
O'Hanley, D. S.: Fault-related phenomena associated with hydration and
serpentine recrystallization during serpentinization, Can. Mineral.,
29, 21–35, 1991.
Rinaudo, C., Gastaldi, D., and Belluso, E.: Characterization of chrysotile,
antigorite and lizardite by FT-Raman spectroscopy, Can. Mineral.,
41, 883–890, 2003.
Trittschack, R., Grobéty, B., and Koch-Müller, M.: In situ
high-temperature Raman and FTIR spectroscopy of the phase transformation of
lizardite, Am. Mineral., 97, 1965–1976, 2012.
Viti, C.: Serpentine minerals discrimination by thermal analysis, Am.
Mineral., 95, 631–638, 2010.
Viti, C. and Hirose, T.: Dehydration reactions and micro-nanostructures in
experimentally-deformed serpentinites, Contr. Mineral. Petrol., 157, 327–338,
2009.
Viti, C. and Mellini, M.: Vein antigorites from Elba Island, ltaly, Eur. J.
Mineral., 8, 423–434, 1996.
Viti, C. and Mellini, M.: Contrasting compositions in coexisting chrysotile
and lizardite in veins from Elba, Italy, Eur. J. Mineral., 9, 585–596, 1997.
Viti, C. and Mellini, M.: Mesh textures and bastites in the Elba retrograde
serpentinites, Eur. J. Mineral., 10, 1341–1359, 1998.
Wicks, F. J. and Chatfield, E. J.: Scrolling of thin crystals of lizardite:
an expression of internal stress, Can. Mineral., 43, 199–2004, 2005.
Wicks, F. J. and Whittaker, E. J. W.: A reappraisal of the structures
of the serpentine minerals, Can. Mineral., 13, 227–243, 1975.
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.
Unusually large lizardite (Lz) crystals from Monte Fico serpentinites, Elba (Mellini and Viti,...
