Special Issue "Mineral Deposits of Critical Elements"

A special issue of Minerals (ISSN 2075-163X). This special issue belongs to the section "Mineral Geochemistry and Geochronology".

Deadline for manuscript submissions: 30 June 2019

Special Issue Editor

Guest Editor
Prof. Dr. Joan Carles Melgarejo Draper

Departament de Mineralogia, Petrologia i Geologia Aplicada, Facultat de Geologia, Universitat de Barcelona (UB), Martí i Franquès s/n, 08028 Barcelona, Catalonia, Spain
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Interests: mineralogy; mineral deposits; critical elements

Special Issue Information

Dear Colleagues,

The strategic and economic interests in some critical elements have drastically increased in the last few years. However, these growing interests have been often decoupled from the enhancement of our understanding of the associated mineral deposits. For many years, what are meant nowadays strategic commodities had been considered mineralogical oddities and less-than-desirable published information exists about the mechanisms of concentration of these elements in nature. Most potential ore minerals are unfamiliar to most geologists, the mineralogy of some important deposits is not well characterized, and even some phases are not established as mineral species yet. A better understanding of the mechanisms of concentration of critical elements and their mineralogical expression will favour their exploration and the development of improved mineral processing schemes. Therefore, the aim of this Special Issue is to provide a contribution to the state of the art of the ore deposits hosting critical elements, mainly from a mineralogical point of view.

Prof. Dr. Joan Carles Melgarejo Draper
Guest Editor

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Keywords

  • Ore deposits
  • Critical elements
  • Critical raw materials
  • Model
  • Mineralogy
  • Mineral characterization
  • Mineral assemblage
  • Fluid inclusions
  • Isotopes
  • Geochemistry
  • Nb
  • Ta
  • Li
  • Be
  • Ga
  • In
  • Ge
  • W
  • Sb
  • REE
  • Co
  • PGE

Published Papers (8 papers)

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Research

Open AccessArticle MVT-Like Fluorite Deposits and Oligocene Magmatic-Hydrothermal Fluorite–Be–U–Mo–P–V Overprints in Northern Coahuila, Mexico
Minerals 2019, 9(1), 58; https://doi.org/10.3390/min9010058
Received: 5 December 2018 / Revised: 10 January 2019 / Accepted: 11 January 2019 / Published: 18 January 2019
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Abstract
The formation of most fluorite deposits in northern Coahuila (NE Mexico) is explained by MVT models, and is a part of the metallogenic province of northeastern Mexico. However, fluorite skarn deposits also occur in the same region, and there is evidence for late [...] Read more.
The formation of most fluorite deposits in northern Coahuila (NE Mexico) is explained by MVT models, and is a part of the metallogenic province of northeastern Mexico. However, fluorite skarn deposits also occur in the same region, and there is evidence for late hydrothermal manifestations with no clear origin and evolution. The latter are the main focus of this study; in particular, F–Be–U–Mo–V–P stringers in the Aguachile-Cuatro Palmas area that overprint preexisting fluorite mantos. The region experienced the emplacement of several intrusives during the Eocene and the Oligocene that are collectively grouped into the East Mexico Alkaline Province (EMAP) and postdate MVT-like deposits. Some of these intrusives have associated skarn deposits; most of them are polymetallic, but the unusual El Pilote deposit contains fluorite mineralisation that was remobilised from MVT-like deposits. The formation of the Aguachile deposit (and, collectively, part of the Cuatro Palmas deposit) has been attributed to a shallow retrograde skarn model. The Cuatro Palmas and Las Alicias fluorite deposits consist of MVT-like deposits overprinted by late hydrothermal fluorite mineralisation rich in Be–U–Mo–V–P, and the Aguachile deposit consists entirely of the latter type. The systematic fluid inclusion study of MVT-like, skarn, and late hydrothermal fluorite deposits reveals a very different distribution of temperature and salinity data that allows the discrimination of mineralising fluids for the type of deposit. MVT-like deposits were formed by fluids with temperatures of homogenisation that range between 50 °C and 152 °C and salinities between 5 and 15.5 wt.% NaCl equivalent. The El Pilote fluorite skarn was formed by fluids with temperatures of homogenisation that range between 78 °C and 394 °C and salinities between 5 and 34 wt.% NaCl equivalent, and include CaCl2-rich brines with salinities that range between 24.5 and 29.1 wt.% CaCl2. Late shallow fluorite–Be–U–Mo–V–P hydrothermal deposits were formed by fluids with temperatures of homogenisation that range between 70 °C and 180 °C and salinities between 0.9 and 3.4 wt.% NaCl equivalent; the sole exception to the above is the La Fácil deposit, with salinities that range between 7.9 and 8.8 wt.% NaCl equivalent. While temperatures of homogenisation are similar between MVT-like and late hydrothermal deposits, and both even have hydrocarbon-rich fluid inclusion associations, the salinity of late deposits is similar to that of retrograde skarn fluids, although further diluted. However, homogenisation temperatures tend to be higher in late hydrothermal than in MVT-like deposits, thus making them more similar to retrograde skarn fluids. Although this characteristic cannot solely establish a genetic link between a retrograde skarn model and late hydrothermal deposits in the study area, the characteristics of fluids associated with the latter separate these deposits from those ascribed to an MVT-like model. Assuming that mineralising fluids for late fluorite–Be–U–Mo–V–P hydrothermal deposits may correspond to a retrograde skarn (or “epithermal”) deposit, the source for fluorine may be either from (A) the dissolution of earlier formed MVT-like deposits, (B) the entrainment of remaining F-rich basinal brines, or (C) hydrothermal fluids exsolved from highly evolved magmas. Possibilities A and B are feasible due to a hypothetical situation similar to the El Pilote skarn, and due to the occurrence of hydrocarbon-rich fluid inclusions at the La Fácil deposit. Possibility C is feasible because intrusive bodies related to highly evolved magmas would have provided other highly lithophile elements like Be, U and Mo upon the exsolution of their hydrothermal fluids. Such intrusive bodies occur in both study areas, and are particularly conspicuous at the Aguachile collapse structure. Full article
(This article belongs to the Special Issue Mineral Deposits of Critical Elements)
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Open AccessArticle Giant Fluorite Mineralization in Central Mexico by Means of Exceptionally Low Salinity Fluids: An Unusual Style among MVT Deposits
Minerals 2019, 9(1), 35; https://doi.org/10.3390/min9010035
Received: 27 November 2018 / Revised: 22 December 2018 / Accepted: 26 December 2018 / Published: 11 January 2019
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Abstract
The origin of the mineralization at the world-class Las Cuevas (the largest single fluorite deposit in the world) has been historically disputed, essentially between skarn-related and Mississippi Valley Type (MVT) models. A systematic study of fluid inclusions in these deposits revealed that they [...] Read more.
The origin of the mineralization at the world-class Las Cuevas (the largest single fluorite deposit in the world) has been historically disputed, essentially between skarn-related and Mississippi Valley Type (MVT) models. A systematic study of fluid inclusions in these deposits revealed that they were formed by low temperature (49 to 177 °C) and low salinity (0 to 1.9 wt % NaCl equiv) fluids. The obtained δ13C (between −2.39 and 0.20‰ VPDB) and δ18O (between −14.03 and −7.37‰ VPDB) data from local host limestones agreed with regionally representative values in the literature. The obtained δ13C (between −15.60 and −12.99‰ VPDB) and δ18O (between −5.56 and −1.84‰ VPDB) data from hydrothermal calcite associated with fluorite mineralization indicated that the isotopic composition of hydrothermal fluids initially reflected buffering by the host rocks, and then recorded the interaction between meteoric water and basinal brines. It is likely that such processes occurred with concurrent maturation of organic matter, and that the obtained compositions may also have recorded a thermal effect on the local limestones. Halogen geochemical studies in inclusion fluids showed a distribution that suggests that solutes in mineralizing fluids were due to scavenging of Na+ and Cl through water–rock interaction or halite dissolution, and that secondary sources would have been the evaporation or infiltration of seawater. The basinal brines with which the formation of these deposits was associated were massively diluted by deeply evolved meteoric water, thus making a significant fluorine input by basinal brines unlikely. Fluorine would have been provided by local groundwater through its interaction with Oligocene topaz rhyolites and other F-rich volcanic and hypabyssal rocks. Such a possibility is supported by present-day groundwater, which presents a regional endemic case of fluorosis. The precipitation of fluorite is possible at low temperatures (at which the solubility of this mineral is very low) by means of chemical reactions and physical interactions among very diluted F-poor basinal brines, F-rich groundwater, and host carbonate rocks. The latter systematically experienced hydrothermal karstification, which would have provided Ca2+ for reaction with F and resulted in the precipitation of fluorite. This scenario stands for a depositional model that recalls those proposed for MVT and associated industrial mineral deposits, but is distinct from common models with regard to the primal source for fluorine and the extremely low salinities of inclusion fluids. Full article
(This article belongs to the Special Issue Mineral Deposits of Critical Elements)
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Open AccessArticle Geochemistry and Mineralogy of Rare Earth Elements (REE) in Bauxitic Ores of the Catalan Coastal Range, NE Spain
Minerals 2018, 8(12), 562; https://doi.org/10.3390/min8120562
Received: 8 October 2018 / Revised: 26 November 2018 / Accepted: 27 November 2018 / Published: 1 December 2018
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Abstract
Karst bauxite deposits are currently investigated as a new resource for rare earth elements (REE) in order to avoid present and future supply shortfalls of these critical metals. The present work focuses on the geochemistry and mineralogy of the REE in karst bauxite [...] Read more.
Karst bauxite deposits are currently investigated as a new resource for rare earth elements (REE) in order to avoid present and future supply shortfalls of these critical metals. The present work focuses on the geochemistry and mineralogy of the REE in karst bauxite deposits of the Catalan Coastal Range (CCR), NE-Spain. It is revealed that the studied bauxitic ores have a dominant breccia and local ooido-pisoidic and pelitomorphic texture. The bauxitic ores are mostly composed of kaolinite and hematite, as well as of lesser amounts of boehmite, diaspore, rutile and calcite. The mineralogy and major element composition indicate incomplete bauxitization of an argillaceous precursor material possibly derived from the erosion of the Mesozoic Ebro massif paleo-high. The studied bauxites are characterized by ∑REE (including Sc, Y) between 286 and 820 ppm (av. 483 ppm) and light REE to heavy REE (LREE/HREE) ratios up to 10.6. REE are mainly concentrated in phosphate minerals, identified as monazite-(Ce) and xenotime-(Y) of detrital origin and unidentified REE-phosphates of a possible authigenic origin. REE remobilization presumably took place under acidic conditions, whereas REE entrapment in the form of precipitation of authigenic rare earth minerals from percolating solutions was related to neutral to slightly alkaline conditions. During the bauxitization process no significant REE fractionation took place and the REE distribution pattern of the bauxitic ores was governed by the REE budget of the precursor material. Finally, adsorption as a main REE scavenging mechanism in the studied CCR bauxite deposits should not be considered, since the presented data did not reveal significant REE contents in Fe-and Mn-oxyhydroxides and clay minerals. Full article
(This article belongs to the Special Issue Mineral Deposits of Critical Elements)
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Open AccessArticle Rare Earth Elements in Planetary Crusts: Insights from Chemically Evolved Igneous Suites on Earth and the Moon
Minerals 2018, 8(10), 455; https://doi.org/10.3390/min8100455
Received: 5 July 2018 / Revised: 5 October 2018 / Accepted: 8 October 2018 / Published: 16 October 2018
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Abstract
The abundance of the rare earth elements (REEs) in Earth’s crust has become the intense focus of study in recent years due to the increasing societal demand for REEs, their increasing utilization in modern-day technology, and the geopolitics associated with their global distribution. [...] Read more.
The abundance of the rare earth elements (REEs) in Earth’s crust has become the intense focus of study in recent years due to the increasing societal demand for REEs, their increasing utilization in modern-day technology, and the geopolitics associated with their global distribution. Within the context of chemically evolved igneous suites, 122 REE deposits have been identified as being associated with intrusive dike, granitic pegmatites, carbonatites, and alkaline igneous rocks, including A-type granites and undersaturated rocks. These REE resource minerals are not unlimited and with a 5–10% growth in global demand for REEs per annum, consideration of other potential REE sources and their geological and chemical associations is warranted. The Earth’s moon is a planetary object that underwent silicate-metal differentiation early during its history. Following ~99% solidification of a primordial lunar magma ocean, residual liquids were enriched in potassium, REE, and phosphorus (KREEP). While this reservoir has not been directly sampled, its chemical signature has been identified in several lunar lithologies and the Procellarum KREEP Terrane (PKT) on the lunar nearside has an estimated volume of KREEP-rich lithologies at depth of 2.2 × 108 km3. This reservoir therefore offers a prospective location for future lunar REE exploration. Within the context of chemically evolved lithologies, lunar granites are rare with only 22 samples currently classified as granitic. However, these extraterrestrial granites exhibit chemical affinities to terrestrial A-type granites. On Earth, these anorogenic magmatic systems are hosts to U-Th-REE-ore deposits and while to date only U-Th regions of enrichment on the lunar surface have been identified, future exploration of the lunar surface and interior may yet reveal U-Th-REE regions associated with the distribution of these chemically distinct, evolved lithologies. Full article
(This article belongs to the Special Issue Mineral Deposits of Critical Elements)
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Open AccessArticle Petrogenesis of Heavy Rare Earth Element Enriched Rhyolite: Source and Magmatic Evolution of the Round Top Laccolith, Trans-Pecos, Texas
Minerals 2018, 8(10), 423; https://doi.org/10.3390/min8100423
Received: 9 August 2018 / Revised: 11 September 2018 / Accepted: 17 September 2018 / Published: 22 September 2018
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Abstract
The Round Top rhyolite located in Trans-Pecos Texas is enriched in Be, F, Li, Nb, Rb, Sn, Th, U, Y, Zr, and rare earth elements (REEs). REE-bearing minerals are mainly ubiquitous nano-scale accessory phases throughout the groundmass, incorporated in synchysite-group minerals, xenotime-(Y), Y- [...] Read more.
The Round Top rhyolite located in Trans-Pecos Texas is enriched in Be, F, Li, Nb, Rb, Sn, Th, U, Y, Zr, and rare earth elements (REEs). REE-bearing minerals are mainly ubiquitous nano-scale accessory phases throughout the groundmass, incorporated in synchysite-group minerals, xenotime-(Y), Y- and Ce-rich fluorite, and zircon. The rhyolite is peraluminous, high-silica, alkaline (not peralkaline), with elevated heavy rare earth element concentrations and anonymously negative Eu values. Pervasive spongy groundmass and recrystallization textures are consistent with the elevated and remobilized Zr, Th, and Y + HREE (heavy rare earth element) concentrations and a high field strength element (HFSE) soluble, sub-alkalic, F-rich, magmatic system. REE-bearing minerals are present as late-magmatic, interstitial phases and attributed with closed-system, post-magmatic, hydrothermal alteration. Petrogenetic modeling provides scenarios that explain the geochemical evolution and REE complexing behavior in evolved rhyolite magmas, and determines possible source compositions and evolution. Trace element models suggest a system typical of having extensive magmatic differentiation. The resulting rhyolite magma is indicative of a silica-rich magmatic system enriched in H2O, Li, and/or F that could be considered transitional between pure silicate melt and hydrothermal fluid, where fluorine-ligand complexing was prevalent through late magmatic cooling and crystallization processes. Thorough differentiation and high fluorine activity contributed to the late stage crystallization of REE-bearing minerals in the Round Top rhyolite. Full article
(This article belongs to the Special Issue Mineral Deposits of Critical Elements)
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Open AccessArticle The Saint-Honoré Carbonatite REE Zone, Québec, Canada: Combined Magmatic and Hydrothermal Processes
Minerals 2018, 8(9), 397; https://doi.org/10.3390/min8090397
Received: 2 July 2018 / Revised: 22 August 2018 / Accepted: 5 September 2018 / Published: 10 September 2018
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Abstract
The Saint-Honoré carbonatite complex hosts a rare earth element (REE) deposit traditionally interpreted as being produced by late-stage hydrothermal fluids that leached REE from apatite or dolomite found in the early units and concentrated the REE in the late-stage units. New evidence from [...] Read more.
The Saint-Honoré carbonatite complex hosts a rare earth element (REE) deposit traditionally interpreted as being produced by late-stage hydrothermal fluids that leached REE from apatite or dolomite found in the early units and concentrated the REE in the late-stage units. New evidence from deeper units suggest that the Fe-carbonatite was mineralized by a combination of both magmatic and hydrothermal crystallization of rare earth minerals. The upper Fe-carbonatite has characteristics typical of hydrothermal mineralization—polycrystalline clusters hosting bastnäsite-(Ce), which crystallized radially from carbonate or barite crystals, as well as the presence of halite and silicification within strongly brecciated units. However, bastnäsite-(Ce) inclusions in primary magmatic barite crystals have also been identified deeper in the Fe-carbonatite (below 1000 m), suggesting that primary crystallization of rare earth minerals occurred prior to hydrothermal leaching. Based on the intensity of hydrothermal brecciation, Cl depletion at depth and greater abundance of secondary fluid inclusions in carbonates in the upper levels, it is interpreted that hydrothermal activity was weaker in this deepest portion, thereby preserving the original magmatic textures. This early magmatic crystallization of rare earth minerals could be a significant factor in generating high-volume REE deposits. Crystallization of primary barite could be an important guide for REE exploration. Full article
(This article belongs to the Special Issue Mineral Deposits of Critical Elements)
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Open AccessArticle REE and Y Mineralogy of the Krudum Granite Body (Saxothuringian Zone)
Minerals 2018, 8(7), 287; https://doi.org/10.3390/min8070287
Received: 9 April 2018 / Revised: 25 June 2018 / Accepted: 2 July 2018 / Published: 5 July 2018
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Abstract
The Krudum granite body comprises highly fractionated granitic rocks ranging from medium-F biotite granites to high-F, high-P2O5 Li-mica granites. This unique assemblage is an ideal site to continue recent efforts in petrology to characterize the role of zircon, monazite, and [...] Read more.
The Krudum granite body comprises highly fractionated granitic rocks ranging from medium-F biotite granites to high-F, high-P2O5 Li-mica granites. This unique assemblage is an ideal site to continue recent efforts in petrology to characterize the role of zircon, monazite, and xenotime as hosts to rare earth elements (REEs). The granitic rocks of the Krudum body analyzed in this study were found to contain variable concentrations of monazite and zircon, while xenotime was only found in the high-F, high-P2O5 Li-mica granites and in the alkali-feldspar syenites of the Vysoký Kámen stock. Intermediate trends between cheralite and huttonite substitutions are characteristic for analyzed monazite grains from all magmatic suites. The highest concentration of cheralite was found in monazite from the alkali-feldspar syenites (up to 69.3 mol %). The proportion of YPO4 in analyzed xenotime grains ranges from 71 to 84 mol %. Xenotime grains are commonly enriched in heavy rare earth elements (HREEs; 9.3–19.5 wt % HREE2O3) and thorite-coffinite and cheralite exchange was observed. Some xenotime analyses return low totals, suggesting their hydration during post-magmatic alterations. Analyzed zircon from granite suites of the Krudum granite body contains moderate Hf concentrations (1.0–4.7 wt % HfO2; 0.010–0.047 apfu Hf). The highest concentrations of HfO2 were found in zircon from the high-F, high-P2O5 Li-mica granites (1.2–4.7 wt % HfO2). Analyzed zircon grains from the high-F, high-P2O5 Li-mica granites and alkali-feldspar syenites are enriched in P (up to 8.29 wt % P2O5; 0.24 apfu P), Al (0.02–2.0 wt % Al2O3; 0.00–0.08 apfu Al), Ca (up to 3.9 wt % CaO; 0.14 apfu Ca), Y (up to 5.5 wt % Y2O3; 0.10 apfu Y), and Sc (up to 1.17 wt % Sc2O3; 0.03 apfu Sc). Zircon grains from the high-F, high-P2O5 Li-mica granites were sometimes hydrated and fluorized. The concentrations of F in zircon from partly greisenised high-F, high-P2O5 Li-mica granites reached up to 1.2 wt % (0.26 apfu F). Full article
(This article belongs to the Special Issue Mineral Deposits of Critical Elements)
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Open AccessArticle Mineralogical Distribution of Germanium, Gallium and Indium at the Mt Carlton High-Sulfidation Epithermal Deposit, NE Australia, and Comparison with Similar Deposits Worldwide
Minerals 2017, 7(11), 213; https://doi.org/10.3390/min7110213
Received: 13 October 2017 / Revised: 27 October 2017 / Accepted: 31 October 2017 / Published: 5 November 2017
Cited by 3 | PDF Full-text (4946 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
Germanium, gallium and indium are in high demand due to their growing usage in high-tech and green-tech applications. However, the mineralogy and the mechanisms of concentration of these critical elements in different types of hydrothermal ore deposits remain poorly constrained. We investigated the [...] Read more.
Germanium, gallium and indium are in high demand due to their growing usage in high-tech and green-tech applications. However, the mineralogy and the mechanisms of concentration of these critical elements in different types of hydrothermal ore deposits remain poorly constrained. We investigated the mineralogical distribution of Ge, Ga and In at the Mt Carlton high-sulfidation epithermal deposit in NE Australia, using electron probe microanalysis and laser ablation inductively-coupled plasma mass spectrometry. Parageneses from which selected minerals were analyzed include: Stage 1 acid sulfate alteration (alunite), Stage 2A high-sulfidation enargite mineralization (enargite, argyrodite, sphalerite, pyrite, barite), Stage 2B intermediate-sulfidation sphalerite mineralization (sphalerite, pyrite, galena) and Stage 3 hydrothermal void fill (dickite). Moderate to locally high concentrations of Ga were measured in Stage 1 alunite (up to 339 ppm) and in Stage 3 dickite (up to 150 ppm). The Stage 2A ores show enrichment in Ge, which is primarily associated with argyrodite (up to 6.95 wt % Ge) and Ge-bearing enargite (up to 2189 ppm Ge). Co-existing sphalerite has comparatively low Ge content (up to 143 ppm), while Ga (up to 1181 ppm) and In (up to 571 ppm) are higher. Sphalerite in Stage 2B contains up to 611 ppm Ge, 2829 ppm Ga and 2169 ppm In, and locally exhibits fine colloform bands of an uncharacterized Zn-In mineral with compositions close to CuZn2(In,Ga)S4. Barite, pyrite and galena which occur in association with Stage 2 mineralization were found to play negligible roles as carriers of Ge, Ga and In at Mt Carlton. Analyzed reference samples of enargite from seven similar deposits worldwide have average Ge concentrations ranging from 12 to 717 ppm (maximum 2679 ppm). The deposits from which samples showed high enrichment in critical elements in this study are all hosted in stratigraphic sequences that locally contain carbonaceous sedimentary rocks. In addition to magmatic-hydrothermal processes, such rocks could potentially be important for the concentration of critical elements in high-sulfidation epithermal deposits. Full article
(This article belongs to the Special Issue Mineral Deposits of Critical Elements)
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