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16 pages, 6619 KiB

Open AccessArticle

Petrography and Geochemistry of the Leucocratic Rocks in the Ophiolites from the Pollino Massif (Southern Italy)

by Giovanna Rizzo, Roberto Buccione, Michele Paternoster, Salvatore Laurita, Luigi Bloise, Egidio Calabrese, Rosa Sinisi and Giovanni Mongelli

Minerals 2021, 11(11), 1264; https://doi.org/10.3390/min11111264 - 13 Nov 2021

Cited by 1 | Viewed by 2571

Abstract

In the Tethyan realm, leucocratic rocks were recognized as dikes and layers outcropping in the ophiolitic rocks of the Western Alps, in Corsica, and in the Northern Apennines. Several authors have suggested that the origin of leucocratic rocks is associated with partial melting [...] Read more.

In the Tethyan realm, leucocratic rocks were recognized as dikes and layers outcropping in the ophiolitic rocks of the Western Alps, in Corsica, and in the Northern Apennines. Several authors have suggested that the origin of leucocratic rocks is associated with partial melting of cumulate gabbro. Major and trace elements composition and paragenesis provided information about the leucocratic rocks genetic processes. This research aims at disclosing, for the first time, the petrographical and geochemical features of Timpa delle Murge leucocratic rocks, Pollino Massif (southern Italy), in order to discuss their origin and geodynamic significance through a comparison with other Tethyan leucocratic rocks. These rocks are characterized by high amounts of silica with moderate alumina and iron-magnesium contents showing higher potassium contents than plagiogranites, due to plagioclase alteration to sericite. Plagioclase fractionation reflects negative Eu anomalies indicating its derivation from gabbroic crystal mushes. The chondrite normalized REEs patterns suggest the participation of partial melts derived from a metasomatized mantle in a subduction environment. The results reveal some similarities in composition with other Tethyan leucocratic rocks, especially those concerning Corsica and the Northern Alps. These new data provide further clues on the origin of these leucocratic rocks and the Tethyan area geodynamic evolution. Full article

(This article belongs to the Special Issue 10th Anniversary of Minerals: Frontiers of Mineral Science)

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18 pages, 8337 KiB

Open AccessArticle

Bi₈Te₃, the 11-Atom Layer Member of the Tetradymite Homologous Series

by Cristiana L. Ciobanu, Ashley D. Slattery, Nigel J. Cook, Benjamin P. Wade and Kathy Ehrig

Minerals 2021, 11(9), 980; https://doi.org/10.3390/min11090980 - 9 Sep 2021

Cited by 7 | Viewed by 2044

Abstract

Bi₈Te₃ is a member of the tetradymite homologous series, previously shown to be compositionally and structurally distinct from hedleyite, Bi₇Te₃, yet inadequately characterized structurally. The phase is identified in a sample from the Hedley district, British [...] Read more.

Bi₈Te₃ is a member of the tetradymite homologous series, previously shown to be compositionally and structurally distinct from hedleyite, Bi₇Te₃, yet inadequately characterized structurally. The phase is identified in a sample from the Hedley district, British Columbia, Canada. Compositions are documented by electron probe microanalysis and structures are directly imaged using high-angle annular dark field (HAADF) scanning transmission electron microscopy (STEM). Results confirm that Bi₈Te₃ has an 11-atom layer structure, in which three Bi-Bi pairs are placed adjacent to the five-atom sequence (Te-Bi-Te-Bi-Te). Bi₈Te₃ has trigonal symmetry (space group R

\bar{3}

m) with unit cell dimensions of a = ~4.4 Å and c = ~63 Å calculated from measurements on representative electron diffraction patterns. The model is assessed by STEM simulations and EDS mapping, all displaying good agreement with the HAADF STEM imaging. Lattice-scale intergrowths are documented in phases replacing Bi₈Te₃, accounting for the rarity of this phase in nature. These results support prior predictions of crystal structures in the tetradymite homologous series from theoretical modeling and indicate that other phases are likely to exist for future discovery. Tetradymite homologues are mixed-layer compounds derived as one-dimensional superstructures of a basic rhombohedral sub-cell. Each member of the series has a discrete stoichiometric composition and unique crystal structure. Full article

(This article belongs to the Special Issue 10th Anniversary of Minerals: Frontiers of Mineral Science)

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13 pages, 15122 KiB

Open AccessArticle

Coupled Substitutions in Natural MnO(OH) Polymorphs: Infrared Spectroscopic Investigation

by Nikita V. Chukanov, Dmitry A. Varlamov, Igor V. Pekov, Natalia V. Zubkova, Anatoly V. Kasatkin and Sergey N. Britvin

Minerals 2021, 11(9), 969; https://doi.org/10.3390/min11090969 - 6 Sep 2021

Cited by 7 | Viewed by 2926

Abstract

Solid solutions involving natural Mn³⁺O(OH) polymorphs, groutite, manganite, and feitknechtite are characterized and discussed based on original and literature data on the chemical composition, powder and single-crystal X-ray diffraction, and middle-range IR absorption spectra of these minerals. It is shown that [...] Read more.

Solid solutions involving natural Mn³⁺O(OH) polymorphs, groutite, manganite, and feitknechtite are characterized and discussed based on original and literature data on the chemical composition, powder and single-crystal X-ray diffraction, and middle-range IR absorption spectra of these minerals. It is shown that manganite forms two kinds of solid-solution series, in which intermediate members have the general formulae (i) (Mn⁴⁺, Mn³⁺)O(OH,O), with pyrolusite as the Mn⁴⁺O₂ end-member, and (ii) (Mn³⁺, M²⁺)O(OH, H₂O), where M = Mn or Zn. In Zn-substituted manganite from Kapova Cave, South Urals, Russia, the Zn²⁺:Mn³⁺ ratio reaches 1:1 (the substitution of Mn³⁺ with Zn²⁺ is accompanied by the coupled substitution of OH⁻ with H₂O). Groutite forms solid-solution series with ramsdellite Mn⁴⁺O₂. In addition, the incorporation of OH⁻ anions in the 1 × 2 tunnels of ramsdellite is possible. Feitknechtite is considered to be isostructural with (or structurally related to) the compounds (M²⁺, Mn³⁺)(OH, O)₂ (M = Mn, Zn) with a pyrochroite-related layered structure. Full article

(This article belongs to the Special Issue 10th Anniversary of Minerals: Frontiers of Mineral Science)

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21 pages, 8208 KiB

Open AccessArticle

The Mixed-Layer Structures of Ikunolite, Laitakarite, Joséite-B and Joséite-A

by Nigel John Cook, Cristiana L. Ciobanu, Ashley D. Slattery, Benjamin P. Wade and Kathy Ehrig

Minerals 2021, 11(9), 920; https://doi.org/10.3390/min11090920 - 25 Aug 2021

Cited by 9 | Viewed by 2244

Abstract

We used high-angle annular dark field scanning transmission electron microscopy (HAADF STEM) to image the crystal structures of four minerals in the Bi₄X₃ isoseries (X = Te, Se, S), a subgroup of the tetradymite homologous series: ikunolite (Bi₄S [...] Read more.

We used high-angle annular dark field scanning transmission electron microscopy (HAADF STEM) to image the crystal structures of four minerals in the Bi₄X₃ isoseries (X = Te, Se, S), a subgroup of the tetradymite homologous series: ikunolite (Bi₄S₃), laitakarite (Bi₄Se₂S), joséite-B (Bi₄Te₂S), and joséite-A (Bi₄TeS₂). The four minerals are isostructural and interpretable in terms of regular stacking of seven-atom packages: [Bi–S–Bi–S–Bi–S–Bi], [Bi–Se–Bi–S–Bi–Se–Bi], [Bi–Te–Bi–S–Bi–Te–Bi], and [Bi–S–Bi–Te–Bi–S–Bi], respectively. The four phases are mixed-layer structures representing the Bi_2kTe₃ (k = 2) module within the tetradymite series. Diffraction patterns confirm they are seven-fold superstructures of a rhombohedral subcell with c/3 = d~1.89–1.93 Å. Modulation along the d* interval matches calculations of reflection intensity using the fractional shift method for Bi₄X₃. Internal structures can be discerned by high-resolution HAADF STEM imaging and mapping. Paired bismuth atoms are positioned at the outside of each seven-atom layer, giving the minerals a modular structure that can also be considered as being composed of five-atom (X–Bi–X–Bi–X) and two-atom (Bi–Bi) sub-modules. The presence of mixed sites for substituting cations is shown, particularly for Pb. Moreover, Pb may be important in understanding the incorporation of Ag and Au in Bi–chalcogenides. Visualisation of crystal structures by HAADF STEM contributes to understanding relationships between phases in the tetradymite homologous series and will play an invaluable role in the characterization of potential additional members of the series. Full article

(This article belongs to the Special Issue 10th Anniversary of Minerals: Frontiers of Mineral Science)

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15 pages, 10985 KiB

Open AccessArticle

The Role of Calcite Dissolution and Halite Thermal Expansion as Secondary Salt Weathering Mechanisms of Calcite-Bearing Rocks in Marine Environments

by Javier Martínez-Martínez, Anna Arizzi and David Benavente

Minerals 2021, 11(8), 911; https://doi.org/10.3390/min11080911 - 23 Aug 2021

Cited by 8 | Viewed by 2665

Abstract

This research focuses on the analysis of the influence of two secondary salt weathering processes on the durability of rocks exposed to marine environments: chemical dissolution of rock forming minerals and differential thermal expansion between halite and the hosting rock. These processes are [...] Read more.

This research focuses on the analysis of the influence of two secondary salt weathering processes on the durability of rocks exposed to marine environments: chemical dissolution of rock forming minerals and differential thermal expansion between halite and the hosting rock. These processes are scarcely treated in research compared to salt crystallisation. The methodology followed in this paper includes both in situ rock weathering monitoring and laboratory simulations. Four different calcite-bearing rocks (a marble, a microcrystalline limestone and two different calcarenites) were exposed during a year to a marine semiarid environment. Exposed samples show grain detachment, crystal edge corrosion, halite efflorescences and microfissuring. Crystal edge corrosion was also observed after the laboratory simulation during a brine immersion test. Calcite chemical dissolution causes a negligible porosity increase in all the studied rocks, but a significant modification of their pore size distribution. Laboratory simulations also demonstrate the deterioration of salt-saturated rocks during thermal cycles in climatic cabinet. Sharp differences between the linear thermal expansion of both a pure halite crystal and the different studied rocks justify the registered weight loss during the thermal cycles. The feedback between the chemical dissolution and differential thermal expansion, and the salt crystallisation of halite, contribute actively to the rock decay in marine environments. Full article

(This article belongs to the Special Issue 10th Anniversary of Minerals: Frontiers of Mineral Science)

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15 pages, 5246 KiB

Open AccessFeature PaperArticle

Nitrogen under Super-Reducing Conditions: Ti Oxynitride Melts in Xenolithic Corundum Aggregates from Mt Carmel (N. Israel)

by William L. Griffin, Sarah E. M. Gain, Martin Saunders, Olivier Alard, Jeremy Shaw, Vered Toledo and Suzanne Y. O’Reilly

Minerals 2021, 11(7), 780; https://doi.org/10.3390/min11070780 - 18 Jul 2021

Cited by 7 | Viewed by 2529

Abstract

Titanium oxynitrides (Ti(N,O,C)) are abundant in xenolithic corundum aggregates in pyroclastic ejecta of Cretaceous volcanoes on Mount Carmel, northern Israel. Petrographic observations indicate that most of these nitrides existed as melts, immiscible with coexisting silicate and Fe-Ti-C silicide melts; some nitrides may also [...] Read more.

Titanium oxynitrides (Ti(N,O,C)) are abundant in xenolithic corundum aggregates in pyroclastic ejecta of Cretaceous volcanoes on Mount Carmel, northern Israel. Petrographic observations indicate that most of these nitrides existed as melts, immiscible with coexisting silicate and Fe-Ti-C silicide melts; some nitrides may also have crystallized directly from the silicide melts. The TiN phase shows a wide range of solid solution, taking up 0–10 wt% carbon and 1.7–17 wt% oxygen; these have crystallized in the halite (fcc) structure common to synthetic and natural TiN. Nitrides coexisting with silicide melts have higher C/O than those coexisting with silicate melts. Analyses with no carbon fall along the TiN–TiO join in the Ti–N–O phase space, implying that their Ti is a mixture of Ti³⁺ and Ti²⁺, while those with 1–3 at.% C appear to be solid solutions between TiN and Ti_0.75O. Analyses with >10 at% C have higher Ti²⁺/Ti³⁺, reflecting a decrease in fO₂. Oxygen fugacity was 6 to 8 log units below the iron–wüstite buffer, at or below the Ti₂O₃–TiO buffer. These relationships and coexisting silicide phases indicate temperatures of 1400–1100 °C. Ti oxynitrides are probably locally abundant in the upper mantle, especially in the presence of CH₄–H₂ fluids derived from the deeper metal-saturated mantle. Full article

(This article belongs to the Special Issue 10th Anniversary of Minerals: Frontiers of Mineral Science)

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32 pages, 6030 KiB

Open AccessArticle

Trace-Element Geochemistry of Sulfides in Upper Mantle Lherzolite Xenoliths from East Antarctica

by Alexandre V. Andronikov, Irina E. Andronikova and Tamara Sidorinova

Minerals 2021, 11(7), 773; https://doi.org/10.3390/min11070773 - 16 Jul 2021

Cited by 5 | Viewed by 2783

Abstract

Sulfides in upper mantle lherzolite xenoliths from Cretaceous alkaline-ultramafic rocks in the Jetty Peninsula (East Antarctica) were studied for their major and trace-element compositions using SEM and LA-ICP-MS applied in situ. Modal abundance of sulfides is the lowest in Cpx-poor lherzolites ≤ Spl-Grt [...] Read more.

Sulfides in upper mantle lherzolite xenoliths from Cretaceous alkaline-ultramafic rocks in the Jetty Peninsula (East Antarctica) were studied for their major and trace-element compositions using SEM and LA-ICP-MS applied in situ. Modal abundance of sulfides is the lowest in Cpx-poor lherzolites ≤ Spl-Grt lherzolites << Cpx-rich lherzolites. Most sulfides are either interstitial (i-type) or inclusions in rock-forming minerals (e-type) with minor sulfide phases mostly present in metasomatic veinlets and carbonate-silicate interstitial patches (m-type). The main sulfide assemblage is pentlandite + chalcopyrite ± pyrrhotite; minor sulfides are polydymite, millerite, violarite, siegenite, and monosulfide solution (mss). Sulfide assemblages in the xenolith matrix are a product of the subsolidus re-equilibration of primary mss at temperatures below ≤300 °C. Platinum group elements (PGE) abundances suggest that most e-type sulfides are the residues of melting processes and that the i-type sulfides are crystallization products of sulfide-bearing fluids/liquids. The m-type sulfides might have resulted from low-temperature metasomatism by percolating sulfide-carbonate-silicate fluids/melts. The PGE in sulfide record processes are related to partial melting in mantle and intramantle melt migration. Most other trace elements initially partitioned into interstitial sulfide liquid and later metasomatically re-enriched residual sulfides overprinting their primary signatures. The extent of element partitioning into sulfide liquids depends on P, T, fO₂, and host peridotite composition. Full article

(This article belongs to the Special Issue 10th Anniversary of Minerals: Frontiers of Mineral Science)

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23 pages, 9886 KiB

Open AccessArticle

Revisiting the Bøggild Intergrowth in Iridescent Labradorite Feldspars: Ordering, Kinetics, and Phase Equilibria

by Shiyun Jin, Huifang Xu and Seungyeol Lee

Minerals 2021, 11(7), 727; https://doi.org/10.3390/min11070727 - 5 Jul 2021

Cited by 3 | Viewed by 3628

Abstract

The enigmatic Bøggild intergrowth in iridescent labradorite crystals was revisited in light of recent work on the incommensurately modulated structures in the intermediated plagioclase. Five igneous samples and one metamorphic labradorite sample with various compositions and lamellar thicknesses were studied in this paper. [...] Read more.

The enigmatic Bøggild intergrowth in iridescent labradorite crystals was revisited in light of recent work on the incommensurately modulated structures in the intermediated plagioclase. Five igneous samples and one metamorphic labradorite sample with various compositions and lamellar thicknesses were studied in this paper. The lamellar textures were characterized with conventional transmission electron microscopy (TEM) and scanning transmission electron microscopy (STEM). The compositions of individual lamellae were analyzed with high-resolution energy-dispersive X-ray spectroscopy (EDS) mapping and atom probe tomography (APT). The average structure states of the studied samples were also compared with single-crystal X-ray diffraction data (SC-XRD). The Na-rich lamellae have a composition of An_44–48, and the Ca-rich lamellae range from An₅₆ to An₆₃. Significant differences between the lamellar compositions of different samples were observed. The compositions of the Bøggild intergrowth do not only depend on the bulk compositions, but also on the thermal history of the host rock. The implications on the subsolidus phase relationships of the plagioclase feldspar solid solution are discussed. The results cannot be explained by a regular symmetrical solvus such as the Bøggild gap, but they support an inclined two-phase region that closes at low temperature. Full article

(This article belongs to the Special Issue 10th Anniversary of Minerals: Frontiers of Mineral Science)

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29 pages, 29441 KiB

Open AccessArticle

The Relation between Trace Element Composition of Cu-(Fe) Sulfides and Hydrothermal Alteration in a Porphyry Copper Deposit: Insights from the Chuquicamata Underground Mine, Chile

by Constanza Rivas-Romero, Martin Reich, Fernando Barra, Daniel Gregory and Sergio Pichott

Minerals 2021, 11(7), 671; https://doi.org/10.3390/min11070671 - 24 Jun 2021

Cited by 10 | Viewed by 4781

Abstract

Porphyry Cu-Mo deposits are among the world’s largest source of Cu, Mo, and Re, and are also an important source of other trace elements, such as Au and Ag. Despite the fact that chalcopyrite, bornite, and pyrite are the most common sulfides in [...] Read more.

Porphyry Cu-Mo deposits are among the world’s largest source of Cu, Mo, and Re, and are also an important source of other trace elements, such as Au and Ag. Despite the fact that chalcopyrite, bornite, and pyrite are the most common sulfides in this deposit type, their trace element content remains poorly constrained. In particular, little is known about minor and trace elements partitioning into Cu-(Fe) sulfides as a function of temperature and pH of the hydrothermal fluid. In this study, we report a comprehensive geochemical database of chalcopyrite, bornite, and pyrite in the super-giant Chuquicamata porphyry Cu-Mo deposit in northern Chile. The aim of our study, focused on the new Chuquicamata Underground mine, was to evaluate the trace element composition of each sulfide from the different hydrothermal alteration assemblages in the deposit. Our approach combines the electron microprobe analysis (EMPA) and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) of sulfide minerals obtained from six representative drill cores that crosscut the chloritic (propylitic), background potassic, intense potassic, and quartz-sericite (phyllic) alteration zones. Microanalytical results show that chalcopyrite, bornite, and pyrite contain several trace elements, and the concentration varies significantly between hydrothermal alteration assemblages. Chalcopyrite, for example, is a host of Se (≤22,000 ppm), Pb (≤83.00 ppm), Sn (≤68.20 ppm), Ag (≤45.1 ppm), Bi (≤25.9 ppm), and In (≤22.8 ppm). Higher concentrations of Se, In, Pb, and Sn in chalcopyrite are related to the high temperature background potassic alteration, whereas lower concentrations of these elements are associated with the lower temperature alteration types: quartz-sericite and chloritic. Bornite, on the other hand, is only observed in the intense and background potassic alteration zones and is a significant host of Ag (≤752 ppm) and Bi (≤2960 ppm). Higher concentrations of Ag and Sn in bornite are associated with the intense potassic alteration, whereas lower concentrations of those two elements are observed in the background potassic alteration. Among all of the sulfide minerals analyzed, pyrite is the most significant host of trace elements, with significant concentrations of Co (≤1530 ppm), Ni (≤960 ppm), Cu (≤9700 ppm), and Ag (≤450 ppm). Co, Ni, Ag, and Cu concentration in pyrite vary with alteration: higher Ag and Cu concentrations are related to the high temperature background potassic alteration. The highest Co contents are associated with lower temperature alteration types (e.g., chloritic). These data indicate that the trace element concentration of chalcopyrite, bornite, and pyrite changed as a function of hydrothermal alteration is controlled by several factors, including temperature, pH, fO₂, fS₂, and the presence of co-crystallizing phases. Overall, our results provide new information on how trace element partitioning into sulfides relates to the main hydrothermal and mineralization events controlling the elemental budget at Chuquicamata. In particular, our data show that elemental ratios in chalcopyrite (e.g., Se/In) and, most importantly, pyrite (e.g., Ag/Co and Co/Cu) bear the potential for vectoring towards porphyry mineralization and higher Cu resources. Full article

(This article belongs to the Special Issue 10th Anniversary of Minerals: Frontiers of Mineral Science)

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30 pages, 20474 KiB

Open AccessArticle

Mudrock Microstructure: A Technique for Distinguishing between Deep-Water Fine-Grained Sediments

by Shereef Bankole, Dorrik Stow, Zeinab Smillie, Jim Buckman and Helen Lever

Minerals 2021, 11(6), 653; https://doi.org/10.3390/min11060653 - 20 Jun 2021

Cited by 2 | Viewed by 2965

Abstract

Distinguishing among deep-water sedimentary facies has been a difficult task. This is possibly due to the process continuum in deep water, in which sediments occur in complex associations. The lack of definite sedimentological features among the different facies between hemipelagites and contourites presented [...] Read more.

Distinguishing among deep-water sedimentary facies has been a difficult task. This is possibly due to the process continuum in deep water, in which sediments occur in complex associations. The lack of definite sedimentological features among the different facies between hemipelagites and contourites presented a great challenge. In this study, we present detailed mudrock characteristics of the three main deep-water facies based on sedimentological characteristics, laser diffraction granulometry, high-resolution, large area scanning electron microscopy (SEM), and the synchrotron X-ray diffraction technique. Our results show that the deep-water microstructure is mainly process controlled, and that the controlling factor on their grain size is much more complex than previously envisaged. Retarding current velocity, as well as the lower carrying capacity of the current, has an impact on the mean size and sorting for the contourite and turbidite facies, whereas hemipelagite grain size is impacted by the natural heterogeneity of the system caused by bioturbation. Based on the microfabric analysis, there is a disparate pattern observed among the sedimentary facies; turbidites are generally bedding parallel due to strong currents resulting in shear flow, contourites are random to semi-random as they are impacted by a weak current, while hemipelagites are random to oblique since they are impacted by bioturbation. Full article

(This article belongs to the Special Issue 10th Anniversary of Minerals: Frontiers of Mineral Science)

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17 pages, 51678 KiB

Open AccessArticle

Iron-Rich Spherules of Taihu Lake: Origin Hypothesis of Taihu Lake Basin in China

by Shuhao Zuo and Zhidong Xie

Minerals 2021, 11(6), 632; https://doi.org/10.3390/min11060632 - 15 Jun 2021

Cited by 3 | Viewed by 2910

Abstract

In this paper, a detailed mineralogical study on iron-rich spherules in Taihu Lake was carried out, and we present a proposed impact-related origin for these iron-rich spherules. The iron-rich spherical concretions in Taihu Lake occur in a specific silty layer formed around ~7 [...] Read more.

In this paper, a detailed mineralogical study on iron-rich spherules in Taihu Lake was carried out, and we present a proposed impact-related origin for these iron-rich spherules. The iron-rich spherical concretions in Taihu Lake occur in a specific silty layer formed around ~7 ka B.P., sandwiched between an upper lacustrine deposit layer and a lower hard loess layer, and they are widely distributed and are the most abundant iron-rich concretions in that specific layer in the vicinity of Taihu Lake. The spherules are typically ~0.5 to 3 mm in diameter with a shape very similar to a spherical shape but not exactly rounded and have various apparent aerodynamic shapes, such as spherical, cone, spindle, ellipsoidal, elongated and pear-shaped morphologies. SEM imaging shows that there is no central core and no concentric layers in the spherules. Iron-rich spherical concretions are similar to accretionary lapilli and have a typical colloidal structure with abundant angular quartz grains and trace fragments of clays wrapped in fine cements that are mainly goethite with minor clays and carbon particles. The typical nodule-forming mechanism in aqueous sediments does not sufficiently explain the morphology and internal features of the iron-rich spherules of Taihu Lake, whereas the aerosol formation mechanism under the airburst impact origin hypothesis of the Taihu Lake basin may be a better explanation of the unique mineralogy of the spherules. Specifically, airburst impact plumes could be the reaction chambers of the aerosol to form the accretionary lapilli with a colloidal texture for the interior, while a dense shell and semi-plastic morphological features can form in the falling processes from higher altitudes in the plume. Full article

(This article belongs to the Special Issue 10th Anniversary of Minerals: Frontiers of Mineral Science)

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21 pages, 4144 KiB

Open AccessArticle

Rare Earth Element and Incompatible Trace Element Abundances in Emeralds Reveal Their Formation Environments

by Raquel Alonso-Perez and James M. D. Day

Minerals 2021, 11(5), 513; https://doi.org/10.3390/min11050513 - 13 May 2021

Cited by 6 | Viewed by 3445

Abstract

Emeralds require the unusual association of typically compatible elements (Cr, V), with incompatible Be to form, and occur in complex tectonic settings associated with sediments (type IIB; Colombia) or, more commonly, with magmatism and regional metamorphism (IA). Precise rare earth element (REE) and [...] Read more.

Emeralds require the unusual association of typically compatible elements (Cr, V), with incompatible Be to form, and occur in complex tectonic settings associated with sediments (type IIB; Colombia) or, more commonly, with magmatism and regional metamorphism (IA). Precise rare earth element (REE) and incompatible trace element abundances are reported for a global suite of emeralds, enabling the identification of the environments in which they formed. Type IIB emeralds have nearly flat continental crust normalized REE patterns (La/Yb_CC = ~2), consistent with a sedimentary source origin. Type IA emerald REE patterns have upturns in the heavy REE (La/Yb_CC = ~0.3), a feature also shared with South African emeralds occurring in Archaean host rocks. Modeling of type IA emerald compositions indicates that they form from magmatic fluids of sedimentary (S)-type granite melts interacting with Cr, V-rich mafic–ultramafic crustal protoliths. This geochemical signature links emerald formation with continental suture zones. Diamonds, rubies, and sapphires have been considered as ‘plate tectonic gemstones’ based on mineral inclusions within them, or associations with plate tectonic indicators. Emeralds are distinct plate tectonic gemstones, recording geochemical evidence for origin within their mineral structure, and indicating that plate tectonic processes have led to emerald deposit formation since at least the Archaean. Full article

(This article belongs to the Special Issue 10th Anniversary of Minerals: Frontiers of Mineral Science)

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12 pages, 1850 KiB

Open AccessArticle

Biogenic Orthorhombic α-Calcium Formate from Sediments of Alkali Lake, Oregon, USA

by Nikita V. Chukanov, Cesar Menor-Salvan, Vladislav V. Gurzhiy, Alina R. Izatulina, Igor V. Pekov, Marina F. Vigasina, Dmitry A. Ksenofontov and Sergey N. Britvin

Minerals 2021, 11(5), 448; https://doi.org/10.3390/min11050448 - 23 Apr 2021

Cited by 5 | Viewed by 3323

Abstract

Centimeter-sized crystals of orthorhombic calcium formate, α-Ca(HCO₂)₂ from Alkali Lake, Oregon, USA have been studied by means of powder and single-crystal X-ray diffraction analysis, infrared, and Raman spectroscopy. Based on the data on carbon isotope abundance in calcium formate and [...] Read more.

Centimeter-sized crystals of orthorhombic calcium formate, α-Ca(HCO₂)₂ from Alkali Lake, Oregon, USA have been studied by means of powder and single-crystal X-ray diffraction analysis, infrared, and Raman spectroscopy. Based on the data on carbon isotope abundance in calcium formate and associated minerals, it was concluded that the formation of α-Ca(HCO₂)₂ may be a result of a combination of two factors: lake microbial metabolism and anthropogenic pollution with Agent Orange. Possible causes of stability of the low-density tetragonal β-Ca(HCO₂)₂ polymorph (formicaite) in boron ores are discussed. Full article

(This article belongs to the Special Issue 10th Anniversary of Minerals: Frontiers of Mineral Science)

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12 pages, 3222 KiB

Open AccessArticle

Crystal Structure of Moganite and Its Anisotropic Atomic Displacement Parameters Determined by Synchrotron X-ray Diffraction and X-ray/Neutron Pair Distribution Function Analyses

by Seungyeol Lee, Huifang Xu, Hongwu Xu and Joerg Neuefeind

Minerals 2021, 11(3), 272; https://doi.org/10.3390/min11030272 - 7 Mar 2021

Cited by 13 | Viewed by 6115

Abstract

The crystal structure of moganite from the Mogán formation on Gran Canaria has been re-investigated using high-resolution synchrotron X-ray diffraction (XRD) and X-ray/neutron pair distribution function (PDF) analyses. Our study for the first time reports the anisotropic atomic displacement parameters (ADPs) of a [...] Read more.

The crystal structure of moganite from the Mogán formation on Gran Canaria has been re-investigated using high-resolution synchrotron X-ray diffraction (XRD) and X-ray/neutron pair distribution function (PDF) analyses. Our study for the first time reports the anisotropic atomic displacement parameters (ADPs) of a natural moganite. Rietveld analysis of synchrotron XRD data determined the crystal structure of moganite with the space group I2/a. The refined unit-cell parameters are a = 8.7363(8), b = 4.8688(5), c = 10.7203(9) Å, and β = 90.212(4)°. The ADPs of Si and O in moganite were obtained from X-ray and neutron PDF analyses. The shapes and orientations of the anisotropic ellipsoids determined from X-ray and neutron measurements are similar. The anisotropic ellipsoids for O extend along planes perpendicular to the Si-Si axis of corner-sharing SiO₄ tetrahedra, suggesting precession-like movement. Neutron PDF result confirms the occurrence of OH over some of the tetrahedral sites. We postulate that moganite nanomineral is stable with respect to quartz in hypersaline water. The ADPs of moganite show a similar trend as those of quartz determined by single-crystal XRD. In short, the combined methods can provide high-quality structural parameters of moganite nanomineral, including its ADPs and extra OH position at the surface. This approach can be used as an alternative means for solving the structures of crystals that are not large enough for single-crystal XRD measurements, such as fine-grained and nanocrystalline minerals formed in various geological environments. Full article

(This article belongs to the Special Issue 10th Anniversary of Minerals: Frontiers of Mineral Science)

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31 pages, 11418 KiB

Open AccessArticle

Multiscale Microbial Preservation and Biogeochemical Signals in a Modern Hot-Spring Siliceous Sinter Rich in CO₂ Emissions, Krýsuvík Geothermal Field, Iceland

by Jose Javier Álvaro, Mónica Sánchez-Román, Klaas G.J. Nierop and Francien Peterse

Minerals 2021, 11(3), 263; https://doi.org/10.3390/min11030263 - 4 Mar 2021

Cited by 4 | Viewed by 2866

Abstract

The microbial communities inferred in silica sinter rocks, based on multiscale morphological features (fabrics and textures) and the presence of lipid biomarkers and their carbon isotopic composition, are evaluated in the Krýsuvík geothermal area of Iceland. Close to vent environments (T > [...] Read more.

The microbial communities inferred in silica sinter rocks, based on multiscale morphological features (fabrics and textures) and the presence of lipid biomarkers and their carbon isotopic composition, are evaluated in the Krýsuvík geothermal area of Iceland. Close to vent environments (T > 75 °C and pH 1.7‒3), stream floors are capped with homogeneous vitreous crusts and breccia levels, with no distinct recognizable silicified microbes. About 4 m far from the vents (T 75‒60 °C and pH 3‒6) and beyond (T < 60 °C and pH 6‒7.6), microbial sinters, including wavy and palisade laminated and bubble fabrics, differ between abandoned meanders and desiccated ponds. Fabric and texture variances are related to changes in the ratio of filament/coccoid silicified microbes and associated porosity. Coatings of epicellular silica, less than 2 µm thick, favor identification of individual microbial filaments, whereas coalescence of opal spheres into agglomerates precludes recognition of original microbial textures and silicified microbes. Episodic fluctuations in the physico-chemical conditions of surface waters controlled the acidic hydrolysis of biomarkers. Wavy laminated fabrics from pond margins comprise fatty acids, mono- and dialkyl glycerol, mono- and diethers, monoalkyl glycerol esters and small traces of 10-methyl branched C₁₆ and C₁₈ fatty acids and archaeol, indicative of intergrowths of cyanobacteria, Aquificales, and sulfate reducing bacteria and methanogenic archaea. In contrast, wavy laminated fabrics from abandoned meanders and palisade laminated fabrics from ponds differ in their branched fatty acids and the presence vs. absence of bacteriohopanetetrol, reflecting different cyanobacterial contributions. δ¹³C values of biomarkers range from −22.7 to −32.9‰, but their values in the wavy (pond) and bubble fabrics have much wider ranges than those of the wavy (meander), palisade, and vitreous fabrics, reflecting dissolved inorganic carbon (DIC) sources and a decrease in ¹³C downstream outflow channels, with heavier values closer to vents and depleted values in ponds. Full article

(This article belongs to the Special Issue 10th Anniversary of Minerals: Frontiers of Mineral Science)

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17 pages, 5099 KiB

Open AccessArticle

Towards Iron-Titanium Oxide Nanostructures from Ecuadorian Black Mineral Sands

by Karina J. Lagos, Bojan A. Marinkovic, Alexis Debut, Karla Vizuete, Víctor H. Guerrero, Emilio Pardo and Patricia I. Pontón

Minerals 2021, 11(2), 122; https://doi.org/10.3390/min11020122 - 26 Jan 2021

Cited by 9 | Viewed by 2971

Abstract

Ecuadorian black mineral sands were used as starting material for the production of iron-titanium oxide nanostructures. For this purpose, two types of mineral processing were carried out, one incorporating a pre-treatment before conducting an alkaline hydrothermal synthesis (NaOH 10 M at 180 °C [...] Read more.

Ecuadorian black mineral sands were used as starting material for the production of iron-titanium oxide nanostructures. For this purpose, two types of mineral processing were carried out, one incorporating a pre-treatment before conducting an alkaline hydrothermal synthesis (NaOH 10 M at 180 °C for 72 h), and the other prescinding this first step. Nanosheet-assembled flowers and nanoparticle agglomerates were obtained from the procedure including the pre-treatment. Conversely, nanobelts and plate-like particles were prepared by the single hydrothermal route. The nanoscale features of the product morphologies were observed by scanning electron microscopy (SEM) and transmission electron microscopy (TEM) analyses. The ilmenite and hematite molar fractions, within the ilmenite-hematite solid solution, in the as-synthetized samples were estimated by Brown’s approach using the computed values of unit-cell volumes from Le Bail adjustments of X-ray powder diffraction (XRPD) patterns. The resulting materials were mainly composed of Fe-rich ilmenite-hematite solid solutions (hematite molar contents ≥0.6). Secondary phases, which possibly belong to lepidocrocite-like or corrugated titanate structures, were also identified. The current study demonstrated the feasibility of employing Ecuadorian mineral resources as low-cost precursors to synthesize high-added-value nanostructures with promising applications in several fields. Full article

(This article belongs to the Special Issue 10th Anniversary of Minerals: Frontiers of Mineral Science)

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19 pages, 3923 KiB

Open AccessArticle

A Possible Radiation-Induced Transition from Monazite-(Ce) to Xenotime-(Y)

by M. Mashrur Zaman and Sytle M. Antao

Minerals 2021, 11(1), 16; https://doi.org/10.3390/min11010016 - 25 Dec 2020

Cited by 5 | Viewed by 2576

Abstract

This study examines two pegmatitic monazite samples (2a and 4b, these numbers are related to a previous study) to determine their crystal chemistry and effects of internal radiation damage using synchrotron high-resolution powder X-ray diffraction and electron-probe micro-analysis. Both the huttonite and cheralite [...] Read more.

This study examines two pegmatitic monazite samples (2a and 4b, these numbers are related to a previous study) to determine their crystal chemistry and effects of internal radiation damage using synchrotron high-resolution powder X-ray diffraction and electron-probe micro-analysis. Both the huttonite and cheralite substitutions are discussed. Rietveld structure refinement of sample 2a shows three different phases [2a = monazite-(Ce), 2b = monazite-(Ce), and 2c = xenotime-(Y)] with distinct structural parameters. The changes among the unit-cell parameters between the two monazite-(Ce) phases is more pronounced in the a followed by the b and c unit-cell parameters. Sample 4a is a single-phase monazite-(Sm) that contains 0.164 apfu Th. Phase 2c with space group I4₁/amd arises from redistribution of La, Ce, Pr, Nd, Sm, Gd, Dy, Si, and Y atoms from those in monazite (space group P2₁/n). A possible cause for the phase transition from monazite-(Ce) to xenotime-(Y) is α-radiation events over a long geological time. However, other chemical processes cannot be ruled out as a cause for the transition. Full article

(This article belongs to the Special Issue 10th Anniversary of Minerals: Frontiers of Mineral Science)

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20 pages, 4783 KiB

Open AccessArticle

Mineralogy of an Appinitic Hornblende Gabbro and Its Significance for the Evolution of Rising Calc-Alkaline Magmas

by Georgia Pe-Piper

Minerals 2020, 10(12), 1088; https://doi.org/10.3390/min10121088 - 3 Dec 2020

Cited by 5 | Viewed by 3738

Abstract

The magmatic and sub-solidus evolution of calcic amphiboles and Fe–Ti oxides was investigated in the Neoproterozoic Frog Lake pluton, Nova Scotia, Canada, in order to understand the relationship between the history of hydrous magma and the resulting mineralogy. The pluton occurs as sheet-like [...] Read more.

The magmatic and sub-solidus evolution of calcic amphiboles and Fe–Ti oxides was investigated in the Neoproterozoic Frog Lake pluton, Nova Scotia, Canada, in order to understand the relationship between the history of hydrous magma and the resulting mineralogy. The pluton occurs as sheet-like bodies of hornblende gabbro and hornblendite, with lesser tonalite dykes and granite bodies, interlayed with screens of medium-grade metamorphic country rock. Small, diffuse clots of felsic minerals are present in the gabbro. The subsolidus growth of actinolite occurs in early clinopyroxenes and amphiboles. Ilmenite is the dominant Fe–Ti oxide, as interstitial magmatic crystals. The increase of Mn towards the margin of the ilmenite crystals indicates a gradual increase in oxygen fugacity with time, leading to the precipitation of titanite and ferrohypersthene. The replacement of titanite by ilmenite and ilmenite lamellae in the amphiboles suggests subsequent reducing conditions during the sub-solidus crystallisation. The gabbros in the coeval, but apparently shallower, Jeffers Brook granodiorite laccolith have dominant magnetite and Mg-rich subsolidus amphiboles, which are indicative of high oxygen fugacity. The differences between the two plutons suggest that there was a greater flux of hydrothermal water through the sheet-like architecture of the Frog Lake pluton. Full article

(This article belongs to the Special Issue 10th Anniversary of Minerals: Frontiers of Mineral Science)

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56 pages, 29760 KiB

Open AccessReview

Straight to Low-Sinuosity Drainage Systems in a Variscan-Type Orogen—Constraints from Tectonics, Lithology and Climate

by Harald G. Dill, Andrei Buzatu and Sorin-Ionut Balaban

Minerals 2021, 11(9), 933; https://doi.org/10.3390/min11090933 - 27 Aug 2021

Cited by 9 | Viewed by 3227

Abstract

A holistic-modular approach has been taken to study the evolution of three straight to low-sinuosity drainage systems (=SSS) in an uplifted basement block of the Central European Variscides. The development of the SSS is described by means of a quadripartite model. (1) The [...] Read more.

A holistic-modular approach has been taken to study the evolution of three straight to low-sinuosity drainage systems (=SSS) in an uplifted basement block of the Central European Variscides. The development of the SSS is described by means of a quadripartite model. (1) The geological framework of the SSS: Forming the lithological and structural features in the bedrock as a result of different temperature, pressure and dynamic-metamorphic processes. (2) Prestage of SSS: Forming the paleo-landscape with a stable fluvial regime as a starting point for the SSS. (3) Proto-SSS: Transition into the metastable fluvial regime of the SSS. (4) Modern SSS: Operation of the metastable fluvial regime Tectonics plays a dual role. Late Paleozoic fold tectonic creates the basis for the studied SSS and has a guiding effect on the development of morphotectonic units during the Neogene and Quaternary. Late Cenozoic fault tectonics triggered the SSS to incise into the Paleozoic basement. The change in the bedrock lithology has an impact on the fluvial and colluvial sediments as well as their landforms. The latter reflects a conspicuous modification: straight drainage system ⇒ higher sinuosity and paired terraces ⇒ hillwash plains. Climate change has an indirect effect controlling via the bedrock the intensity of mechanical and chemical weathering. The impact on the development of the SSS can be assessed as follows: Tectonics >> climate ≅ bedrock lithology. The three parameters cause a facies zonation: (1) wide-and-shallow valley (Miocene), (2) wide-angle V-shaped valley (Plio-Pleistocene), (3) acute-angle V-shaped valley (Pleistocene), (4) V-shaped to U-shaped valleys (Pleistocene-Holocene). Numerical data relevant for the hydrographic studies of the SSS are determined in each reference area: (1) Quantification of fluvial and colluvial deposits along the drainage system, (2) slope angles, (3) degree of sinuosity as a function of river facies, (4) grain size distribution, (5) grain morphological categorization, (6) grain orientation (“situmetry”), (7) channel density, (8) channel/floodplain ratios. Thermodynamic computations (Eh, pH, concentration of solubles) are made to constrain the paleoclimatic regime during formation of the SSS. The current model of the SSS is restricted in its application to the basement of the Variscan-Type orogens, to an intermediate crustal maturity state. Full article

(This article belongs to the Special Issue 10th Anniversary of Minerals: Frontiers of Mineral Science)

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30 pages, 6791 KiB

Open AccessReview

An Overview of the Geochemical Characteristics of Oceanic Carbonatites: New Insights from Fuerteventura Carbonatites (Canary Islands)

by Gabriele Carnevale, Antonio Caracausi, Alessandra Correale, Laura Italiano and Silvio G. Rotolo

Minerals 2021, 11(2), 203; https://doi.org/10.3390/min11020203 - 15 Feb 2021

Cited by 13 | Viewed by 4440

Abstract

The occurrence of carbonatites in oceanic settings is very rare if compared with their continental counterpart, having been reported only in Cape Verde and Canary Islands. This paper provides an overview of the main geochemical characteristics of oceanic carbonatites, around which many debates [...] Read more.

The occurrence of carbonatites in oceanic settings is very rare if compared with their continental counterpart, having been reported only in Cape Verde and Canary Islands. This paper provides an overview of the main geochemical characteristics of oceanic carbonatites, around which many debates still exist regarding their petrogenesis. We present new data on trace elements in minerals and whole-rock, together with the first noble gases isotopic study (He, Ne, Ar) in apatite, calcite, and clinopyroxene from Fuerteventura carbonatites (Canary Islands). Trace elements show a similar trend as Cape Verde carbonatites, almost tracing the same patterns on multi-element and REE abundance diagrams. ³He/⁴He isotopic ratios of Fuerteventura carbonatites reflect a shallow (sub-continental lithospheric mantle, SCLM) He signature in their petrogenesis, and they clearly differ from Cape Verde carbonatites, i.e., fluids from a deep and low degassed mantle with a primitive plume-derived He signature are involved in their petrogenesis. Full article

(This article belongs to the Special Issue 10th Anniversary of Minerals: Frontiers of Mineral Science)

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19 pages, 7177 KiB

Open AccessReview

A Series of Data-Driven Hypotheses for Inferring Biogeochemical Conditions in Alkaline Lakes and Their Deposits Based on the Behavior of Mg and SiO₂

by Jasmine E. Chase, Maria L. Arizaleta and Benjamin M. Tutolo

Minerals 2021, 11(2), 106; https://doi.org/10.3390/min11020106 - 22 Jan 2021

Cited by 18 | Viewed by 3149

Abstract

Alkaline (pH > 8.5) lakes have been common features of Earth’s surface environments throughout its history and are currently among the most biologically productive environments on the planet. The chemistry of alkaline lakes favors the deposition of aluminum-poor magnesian clays (e.g., sepiolite, stevensite, [...] Read more.

Alkaline (pH > 8.5) lakes have been common features of Earth’s surface environments throughout its history and are currently among the most biologically productive environments on the planet. The chemistry of alkaline lakes favors the deposition of aluminum-poor magnesian clays (e.g., sepiolite, stevensite, and kerolite) whose chemistry and mineralogy may provide a useful record of the biogeochemistry of the lake waters from which they were precipitated. In this forward-looking review, we present six data-driven, testable hypotheses devoted to furthering our understanding of the biogeochemical conditions in paleolake waters based on the geochemical behavior of Mg and SiO₂. In the development of these hypotheses, we bring together a compilation of modern lake water chemistry, recently published and new experimental data, and empirical, thermodynamic, and kinetic relationships developed from these data. We subdivide the hypotheses and supporting evidence into three categories: (1) interpreting paleolake chemistry from mineralogy; (2) interpreting the impact of diatoms on alkaline lake sedimentation; and (3) interpreting depositional mineralogy based on water chemistry. We demonstrate the need for further investigation by discussing evidence both for and against each hypothesis, which, in turn, highlights the gaps in our knowledge and the importance of furthering our understanding of the relevant geological and biological systems. The focused testing of these hypotheses against modern occurrences and the geologic record of alkaline lakes can have profound implications for the interpretation of the paleo-biogeochemistry and paleohabitability of these systems on Earth and beyond. Full article

(This article belongs to the Special Issue 10th Anniversary of Minerals: Frontiers of Mineral Science)

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