Articles | Volume 35, issue 5
https://doi.org/10.5194/ejm-35-737-2023
© 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-35-737-2023
© Author(s) 2023. This work is distributed under
the Creative Commons Attribution 4.0 License.
the Creative Commons Attribution 4.0 License.
Research article
| 
04 Sep 2023
Research article |
| 04 Sep 2023
| 04 Sep 2023
The effect of chemical variability and weathering on Raman spectra of enargite and fahlore
Khulan Berkh
CORRESPONDING AUTHOR
Federal Institute for Geosciences and Natural Resources, Stilleweg 2,
30655 Hanover, Germany
Juraj Majzlan
Institute of Geosciences, Friedrich Schiller University, Burgweg 11,
07749 Jena, Germany
Jeannet A. Meima
Federal Institute for Geosciences and Natural Resources, Stilleweg 2,
30655 Hanover, Germany
Jakub Plášil
Institute of Physics of the CAS, Na Slovance 1999/2, 18200 Prague 8,
Czech Republic
Dieter Rammlmair
Institute of Mineralogy, Leibniz University Hannover, Callinstraße
3–9, 30167 Hanover, Germany
Related authors
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.
Juraj Majzlan, Anna Reichstein, Patrick Haase, Martin Števko, Jiří Sejkora, and Edgar Dachs
Eur. J. Mineral., 36, 31–54, https://doi.org/10.5194/ejm-36-31-2024, https://doi.org/10.5194/ejm-36-31-2024, 2024
Short summary
Short summary
Minerals formed by weathering of toxic materials, of either natural or human origin, act as storage containers for toxic elements. In this work, we investigated properties of common minerals which store and release arsenic in the environment. The data presented here will allow for improved modeling of the polluted sites and for better remediation strategies that could be applied to minimize the impact of the pollution on the environment.
Juraj Majzlan, Alexandra Plumhoff, Martin Števko, Gwladys Steciuk, Jakub Plášil, Edgar Dachs, and Artur Benisek
Eur. J. Mineral., 35, 157–169, https://doi.org/10.5194/ejm-35-157-2023, https://doi.org/10.5194/ejm-35-157-2023, 2023
Short summary
Short summary
This research was done to understand how toxic elements, such as copper or arsenic, move through the environment. The data presented here can be used to model mobility of such elements and to improve remediation strategies at sites contaminated by mining.
Patrick Haase, Stefan Kiefer, Kilian Pollok, Petr Drahota, and Juraj Majzlan
Eur. J. Mineral., 34, 493–506, https://doi.org/10.5194/ejm-34-493-2022, https://doi.org/10.5194/ejm-34-493-2022, 2022
Short summary
Short summary
Stannite decomposition leads to the precipitation of an amorphous and metastable Sn–Fe–As-rich phase. With ageing, goethite and cassiterite crystallize from the precursor and mark the end of the weathering cycle. Other elements are lost in the initial stage of weathering (e.g. Zn, S) or after full oxidation of the sulfidic material (e.g. Cu, Ag). Electron microprobe (EMP) and transmission electron microscopy (TEM) analyses were performed to witness the mobility of the released elements.
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.
Luboš Vrtiška, Jaromír Tvrdý, Jakub Plášil, Jiří Sejkora, Radek Škoda, Nikita V. Chukanov, Andreas Massanek, Jan Filip, Zdeněk Dolníček, and František Veselovský
Eur. J. Mineral., 34, 223–238, https://doi.org/10.5194/ejm-34-223-2022, https://doi.org/10.5194/ejm-34-223-2022, 2022
Short summary
Short summary
The study of the original material of beraunite from the type locality Hrbek, Czech Rep., from collections of the TU Bergakademie Freiberg (Germany) and National Museum Prague (Czech Republic) proved the identity of the minerals beraunite and eleonorite. Because the name beraunite has priority, we consider the name eleonorite to be redundant and proposed to abolish it. The proposal 21-D approved by the IMA discredited eleonorite and accepted the formula of beraunite Fe3+6(PO4)4O(OH)4·6H2O.
Juraj Majzlan, Stefan Kiefer, Kristina Lilova, Tamilarasan Subramani, Alexandra Navrotsky, Edgar Dachs, and Artur Benisek
Eur. J. Mineral., 33, 357–371, https://doi.org/10.5194/ejm-33-357-2021, https://doi.org/10.5194/ejm-33-357-2021, 2021
Short summary
Short summary
Chapmanite is a seemingly rare mineral, a silicate of the elements iron and antimony. In this work, we evaluated how stable and how soluble this mineral is. The goal was to determine if this mineral can store the toxic element antimony. Our results show that it is possible, but its formation in nature is hindered and slow. Yet, in some special environments, it could store and keep antimony over longer time.
Pavel Škácha, Jiří Sejkora, Jakub Plášil, Zdeněk Dolníček, and Jana Ulmanová
Eur. J. Mineral., 33, 175–187, https://doi.org/10.5194/ejm-33-175-2021, https://doi.org/10.5194/ejm-33-175-2021, 2021
Short summary
Short summary
Grimmite, sulfide of cobalt and nickel, is the new mineral for the mineralogical system.
Alexandra M. Plumhoff, Jakub Plášil, Edgar Dachs, Artur Benisek, Jiří Sejkora, Martin Števko, Mike S. Rumsey, and Juraj Majzlan
Eur. J. Mineral., 32, 285–304, https://doi.org/10.5194/ejm-32-285-2020, https://doi.org/10.5194/ejm-32-285-2020, 2020
Aileen Meier, Anne Kastner, Dennis Harries, Maria Wierzbicka-Wieczorek, Juraj Majzlan, Georg Büchel, and Erika Kothe
Biogeosciences, 14, 4867–4878, https://doi.org/10.5194/bg-14-4867-2017, https://doi.org/10.5194/bg-14-4867-2017, 2017
Short summary
Short summary
Biomineralization of (magnesium) calcite and vaterite by bacterial isolates was observed using isolates from limestone associated groundwater, rock and soil. More than 92 % of isolates could form carbonates with different crystal macromorphologies. Using different conditions like varying temperature, pH or media components but also cocultivation to test for collaborative effects of sympatric bacteria, mechanisms of calcium carbonate formation were studied.
Wilhelm Nikonow and Dieter Rammlmair
Geosci. Instrum. Method. Data Syst., 6, 429–437, https://doi.org/10.5194/gi-6-429-2017, https://doi.org/10.5194/gi-6-429-2017, 2017
Short summary
Short summary
This work describes a new approach to use fast X-ray fluorescence mapping as a tool for automated mineralogy applied on thin sections of plutonic rocks. Using a supervised classification of the spectral information, mineral maps are obtained for modal mineralogy and image analysis. The results are compared to a conventional method for automated mineralogy, which is scanning electron microscopy with mineral liberation analyzer, showing a good overall accuracy of 76 %.
E. Schütze, A. Weist, M. Klose, T. Wach, M. Schumann, S. Nietzsche, D. Merten, J. Baumert, J. Majzlan, and E. Kothe
Biogeosciences, 10, 3605–3614, https://doi.org/10.5194/bg-10-3605-2013, https://doi.org/10.5194/bg-10-3605-2013, 2013
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)
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
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)
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.
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, 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
Short summary
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.
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
Apopei, A., Damian, G., Buzgar, N., Buzatu, A., Andráš, P., and
Milovská, S.: The determination of the
Ásbjörnsson, J., Kelsall, G. H., Pattrick, R. A. D., Vaughan, D. J.,
Wincott, P. L., and Hope, G. A.: Electrochemical and Surface Analytical
Studies of Enargite in Acid Solution, J. Electrochem.
Soc., 151, E250, https://doi.org/10.1149/1.1756892, 2004.
Batanova, V. G., Sobolev, A. V., and Kuzmin, D. V.: Trace element analysis
of olivine: High precision analytical method for JEOL JXA-8230 electron
probe microanalyser, Chem. Geol., 419, 149–157,
https://doi.org/10.1016/j.chemgeo.2015.10.042, 2015.
Biagioni, C., George, L., Cook, N., Makovicky, E., Moëlo, Y., Pasero,
M., Sejkora, J., Stanley, C., Welch, M., and Bosi, F.: The tetrahedrite
group: Nomenclature and classification, Am. Mineral., 105, 109–122,
https://doi.org/10.2138/am-2020-7128, 2020.
Chen, Y., Zhu, S., Taskinen, P., Peng, N., Peng, B., Jokilaakso, A., Liu,
H., Liang, Y., Zhao, Z., and Wang, Z.: Treatment of high-arsenic copper
smelting flue dust with high copper sulfate: Arsenic separation by low
temperature roasting, Miner. Eng., 164, 106796,
https://doi.org/10.1016/j.mineng.2021.106796, 2021.
Da Pelo, S.: Environmental geochemistry and mineralogy of active and abandoned mine sites, PhD Thesis in Earth Sciences, Cagliari-Genova-Torino, 1998 (in Italian, extended abstract in English in Plinius 21, 70–74, 1999).
Davis, A., Ruby, M. V., and Bergstrom, P. D.: Bioavailability of arsenic and
lead in soils from the Butte, Montana, mining district, Environ.
Sci. Technol., 26, 461–468, https://doi.org/10.1021/es00027a002, 1992.
Deyell-Wurst, C. and Hedenquist, J.: Trace element geochemistry of enargite
in the Mankayan district, PHILIPPINES, Econ. Geol., 106, 1465–1478,
https://doi.org/10.2113/econgeo.106.8.1465, 2011.
Dold, B.: Sustainability in metal mining: from exploration, over processing
to mine waste management, Rev. Environ. Sci.
Bio, 7, 275–285, https://doi.org/10.1007/s11157-008-9142-y, 2008.
Dutrizac, J. E. and MacDonald, R. J. C.: The kinetics of dissolution of
enargite in acidified ferric sulphate solutions, Can. Metall.
Quart., 11, 469–476, https://doi.org/10.1179/cmq.1972.11.3.469, 1972.
Elkina, Y. A., Melnikova, E. A., Melamud, V. S., and Bulaev, A. G.:
Bioleaching of Enargite and Tennantite by Moderately Thermophilic
Acidophilic Microorganisms, Microbiology, 89, 413–424,
https://doi.org/10.1134/S0026261720040050, 2020.
Elsener, B., Atzei, D., Fantauzzi, M., and Rossi, A.: Electrochemical and
XPS surface analytical studies on the reactivity of enargite, Eur. J. Mineral., 19, 353–361, https://doi.org/10.1127/0935-1221/2007/0019-1729, 2007.
Fullston, D., Fornasiero, D., and Ralston, J.: Zeta potential study of the
oxidation of copper sulfide minerals, Colloids Surface. A, 146, 113–121, 1999.
Gow, R., Huang, H., and Young, C.: Utility of mass-balanced EH-pH diagrams I
– Applications of Gibbs' Phase Rule, 2014 SME Annual Meeting and Exhibit,
SME 2014: Leadership in Uncertain Times, Miner. Metall. Proc., 33, 794–800, https://doi.org/10.19150/mmp.6622,
2014.
Haase, P., Kiefer, S., Pollok, K., Drahota, P., and Majzlan, J.: Weathering of stannite–kësterite [Cu2(Fe,Zn)SnS4] and the environmental mobility of the released elements, Eur. J. Mineral., 34, 493–506, https://doi.org/10.5194/ejm-34-493-2022, 2022.
Herreros, O., Quiroz, R., Hernández, M. C., and Viñals, J.:
Dissolution kinetics of enargite in dilute Cl2/Cl− media, Hydrometallurgy,
64, 153–160, https://doi.org/10.1016/S0304-386X(02)00034-8, 2002.
Ishihara, S., Shinoda, K., and Kano, J.: Mechanochemical Treatment to Remove
Arsenic from Copper Ore, Minerals, 9, 349, https://doi.org/10.3390/min9060349, 2019.
Karanovi, L. J., Cvetkovi, L. J., Poleti, D., Bali-uni, T., and Makovicky,
E.: Crystal and absolute structure of enargite from Bor (Serbia), Neues
Jb. Miner. Monat., 2002, 241–253,
https://doi.org/10.1127/0028-3649/2002/2002-0241, 2002.
Kase, K.: Tellurian tennantite from the besshi-type deposits in the
Sambagawa metamorphic belt, Japan, Can. Mineral., 24, 399–404, 1986.
Kharbish, S. and Jelen, S.: Raman spectroscopy of the Pb-Sb sulfosalts
minerals: Boulangerite, jamesonite, robinsonite and zinkenite, Vib.
Spectrosc., 85, 157–166, https://doi.org/10.1016/j.vibspec.2016.04.016, 2016.
Kharbish, S., Libowitzky, E., and Beran, A.: The effect of As-Sb
substitution in the Raman spectra of tetrahedrite-tennantite and
pyrargyrite-proustite solid solutions, Eur. J. Mineral., 19,
567–574, https://doi.org/10.1127/0935-1221/2007/0019-1737, 2007.
Lattanzi, P., Da Pelo, S., Musu, E., Atzei, D., Elsener, B., Fantauzzi, M.,
and Rossi, A.: Enargite oxidation: A review, Earth-Sci. Rev., 86,
62–88, https://doi.org/10.1016/j.earscirev.2007.07.006, 2008.
Li, D., Bancroft, G. M., Kasrai, M., Fleet, M. E., Feng, X. H., Yang, B. X.,
and Tan, K. H.: S K- and L-edge XANES and electronic structure of some
copper sulfide minerals, Phys. Chem. Miner., 21, 317–324,
https://doi.org/10.1007/BF00202096, 1994.
Li, T., Zhang, Y., Zhang, B., Jiao, F., and Qin, W.: Flotation separation of
enargite from complex copper concentrates by selective surface oxidation,
Physicochem. Probl. Mi., 55, 852–864,
https://doi.org/10.5277/ppmp19005, 2019.
Liu, W., Cook, N. J., Ciobanu, C. L., and Gilbert, S. E.: Trace element
substitution and grain-scale compositional heterogeneity in enargite, Ore
Geol. Rev., 111, 103004,
https://doi.org/10.1016/j.oregeorev.2019.103004, 2019.
Long, G., Peng, Y., and Bradshaw, D.: A review of copper–arsenic mineral
removal from copper concentrates, Miner. Eng., 36–38, 179–186,
https://doi.org/10.1016/j.mineng.2012.03.032, 2012.
Long, G., Peng, Y., and Bradshaw, D.: Flotation separation of copper
sulphides from arsenic minerals at Rosebery copper concentrator, Miner.
Eng., 66–68, 207–214, https://doi.org/10.1016/j.mineng.2014.04.003,
2014.
Makovicky, E. and Karup-Møller, S.: Exploratory Studies of Substitutions
in the Tetrahedrite/tennantite–goldfieldite Solid Solution, Can.
Mineral., 55, 233–244, https://doi.org/10.3749/canmin.1600067, 2017.
Makovicky, E., Karanovic, L., Poleti, D., Balic-Zunic, T., and Paar, W.:
Crystal structure of copper-rich unsubstituted tennantite, Cu12.5As4S13,
Can. Mineral., 43, 679–688,
https://doi.org/10.2113/gscanmin.43.2.679, 2005.
Mernagh, T. P. and Trudu, A. G.: A laser Raman microprobe study of some
geologically important sulphide minerals, Chem. Geol., 103, 113–127,
https://doi.org/10.1016/0009-2541(93)90295-T, 1993.
Moëlo, Y., Makovicky, E., Secretary, A., Mozgova, N., Jambor, J., Cook,
N., Pring, A., Paar, W., Nickel, E., Graeser, S., Sven, K.-M., Balic-Zunic,
T., Mumme, W., Vurro, F., Topa, D., Bindi, L., Bente, K., and Shimizu, M.:
Sulfosalt systematics: A review. Report of the sulfosalt sub-committee of
the IMA Commission on Ore Mineralogy, Eur. J. Mineral, 20, 7–46,
https://doi.org/10.1127/0935-1221/2008/0020-1778, 2008.
Nakamoto, K.: Infrared and Raman spectra of inorganic and coordination
compounds. Part A: Theory and applications in inorganic chemistry, John
Wiley & Sons, Inc., New York, 408 pp., ISBN 978-0471163947, 1997.
National Center for Biotechnology Information: PubChem Compound
Summary for CID 177517, Enargite (Cu3(AsS4), https://pubchem.ncbi.nlm.nih.gov/compound/Enargite-_Cu3_AsS4 (last access: 10 October 2022), 2022.
O'Day, P.: Chemistry and Mineralogy of Arsenic, Elements, 2, 77–83,
https://doi.org/10.2113/gselements.2.2.77, 2006.
Padilla, R., Girón, D., and Ruiz, M. C.: Leaching of enargite in
H2SO4–NaCl–O2 media, Hydrometallurgy, 80, 272–279,
https://doi.org/10.1016/j.hydromet.2005.08.006, 2005.
Padilla, R., Aracena, A., and Ruiz, M. C.: Reaction Mechanism and Kinetics
of Enargite Oxidation at Roasting Temperatures, Metall. Mater.
Trans. B, 43, 1119–1126, https://doi.org/10.1007/s11663-012-9675-x, 2012.
Pauling, L.: Crystallography and chemical bonding of sulfide minerals, Min. Soc. Am. Spec. Pap, 3, 125–131, 1970.
Pauling, L. and Weinbaum, S.: The Crystal Structure of Enargite, Cu3AsS4,
Z. Kristallogr., 88, 48–53,
https://doi.org/10.1524/zkri.1934.88.1.48, 1934.
Pfitzner, A. and Bernert, T.: The system Cu3AsS4–Cu3SbS4 and investigations
on normal tetrahedral structures, Z. Kristallogr., 219, 20–26, https://doi.org/10.1524/zkri.219.1.20.25398, 2004.
Pfitzner, A., Evain, M., and Petrícek, V.: Cu12Sb4S13: A
Temperature-Dependent Structure Investigation, Acta Crystallogr. B, 53, 337–345, https://doi.org/10.1107/S0108768196014024, 1997.
Plackowski, C.: Investigation of the surface species formed on enargite in electrochemically controlled oxidising environments and in the presence of flotation collectors, PhD Thesis, School of Chemical Engineering, The University of Queensland, https://doi.org/10.14264/uql.2014.476, 2014.
Plumlee, G.: The environmental geology of mineral deposits, Rev. Econ. Geol., 6A, 71–116, 1999.
Pósfai, M. and Buseck, P.: Relationships between microstructure and
composition in enargite and luzonite, Am. Mineral., 83, 373–382,
https://doi.org/10.2138/am-1998-3-422, 1998.
Rigaku Oxford Diffraction: CrysAlisPro Software system, version 1.171.39.46, Rigaku Corporation, Oxford, UK, 2019.
Rossi, A., Atzei, D., Da Pelo, S., Frau, F., Lattanzi, P., England, K. E.
R., and Vaughan, D. J.: Quantitative X-ray photoelectron spectroscopy study
of enargite (Cu3AsS4) surface, Surf. Interface Anal., 31, 465–470,
https://doi.org/10.1002/sia.1072, 2001.
Rumball, J. A. and Richmond, G. D.: Measurement of oxidation in a base metal
flotation circuit by selective leaching with EDTA, Int. J.
Miner. Process., 48, 1–20, https://doi.org/10.1016/S0301-7516(96)00010-5,
1996.
Sasaki, K., Takatsugi, K., Ishikura, K., and Hirajima, T.: Spectroscopic
study on oxidative dissolution of chalcopyrite, enargite and tennantite at
different pH values, Hydrometallurgy, 100, 144–151,
https://doi.org/10.1016/j.hydromet.2009.11.007, 2010.
Schneiderhöhn, H.: Anleitung zur mikroskopischen bestimmung und untersuchung von erzen und aufbereitungsprodukten besonders im auffallenden licht, Gesellschaft Deutscher Metallhütten- und Bergleute, ISBN 978-0364640548, 1922.
Senior, G. and Trahar, W. J.: The influence of metal hydroxides and
collector on the flotation of chalcopyrite, Int. J. Miner.
Process., 33, 321–341, 1991.
Sillitoe, R. H.: Porphyry Copper Systems*, Econ. Geol., 105, 3–41,
https://doi.org/10.2113/gsecongeo.105.1.3, 2010.
Springer, G.: Compositional variations in enargite and luzonite, Miner.
Deposita, 4, 72–74, 1969.
Takéuchi, Y. and Sadanaga, R.: Structural principles and classification
of sulfosalts, Z. Kristallogr., 130, 346–368, 1969.
Tayebi-Khorami, M., Manlapig, E., Forbes, E., Bradshaw, D., and Edraki, M.:
Selective flotation of enargite from copper sulphides in Tampakan deposit,
Mineral. Eng., 112, 1–10,
https://doi.org/10.1016/j.mineng.2017.06.021, 2017.
Tayebi-Khorami, M., Manlapig, E., Forbes, E., Edraki, M., and Bradshaw, D.:
Effect of surface oxidation on the flotation response of enargite in a
complex ore system, Mineral. Eng., 119, 149–155,
https://doi.org/10.1016/j.mineng.2018.01.024, 2018.
Trudu, A. G. and Knittel, U.: Crystallography, mineral chemistry and chemical nomenclature of goldfieldite, the tellurian member of the tetrahedrite solid-solution series, Can. Mineral., 36, 1115–1137, 1998.
Tuschel, D.: Practical Group Theory and Raman Spectroscopy, Part II:
Application of Polarization, Spectroscopy, 29, 14–22, 2014.
Tuschel, D.: Effect of dopants or impurities on the raman spectrum of the
host crystal, Spectroscopy (Santa Monica), 32, 13–18, 24, 2017.
Viñals, J., Roca, A., Hernández, M. C., and Benavente, O.:
Topochemical transformation of enargite into copper oxide by hypochlorite
leaching, Hydrometallurgy, 68, 183–193,
https://doi.org/10.1016/S0304-386X(02)00200-1, 2003.
Wang, A., Han, J., Guo, L., Yu, J., and Zeng, P.: Database of Standard Raman
Spectra of Minerals and Related Inorganic Crystals, Appl. Spectrosc.,
48, 959–968, 1994.
Welham, N. J.: Mechanochemical processing of enargite (Cu3AsS4),
Hydrometallurgy, 62, 165–173, 2001.
Wilkomirsky, I., Parra, R., Parada, F., Balladares, E., Etcheverry, J., and
Díaz, R.: Partial Roasting of High-Arsenic Copper Concentrates,
Metall. Mater. Trans. B, 51, 2030–2038,
10.1007/s11663-020-01893-x, 2020.
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.
Since As is detrimental to the environment, the As content of ores should be reduced before it...
