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Minerals Down to the Nanoscale: A Glimpse at Ore-Forming Processes

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A special issue of Minerals (ISSN 2075-163X).

Deadline for manuscript submissions: closed (31 May 2019) | Viewed by 54715

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Special Issue Editors

Dr. Cristiana L. Ciobanu

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Guest Editor

School of Chemical Engineering, University of Adelaide, Adelaide, SA 5005, Australia
Interests: ore-forming processes; nanoscale characterisation of ore minerals; microanalysis
Special Issues, Collections and Topics in MDPI journals

Assoc. Prof. Dr. Satoshi Utsunomiya

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Department of Chemistry, Kyushu University, 744 Motooka, Nishi-ku, Fukuoka-shi 819-0395, Japan

Prof. Dr. Martin Reich

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Department of Geology, University of Chile, Plaza Ercilla 803, Santiago, Chile
Interests: economic geology; geochemistry of mineral deposits; hydrothermal systems; nanogeochemistry; sulfide mineralogy

Assist. Prof. Dr. Oliver Plümper

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Department of Earth Sciences, Utrecht University, Princetonlaan 8A, 3584 CB Utrecht, The Netherlands

Special Issue Information

Dear Colleagues,

Minerals form in all types of geological and anthropogenic environments. They often record superimposed geochemical processes as they react with fluids of various origins, or undergo tectonothermal events in terranes with protracted geological histories. Understanding their evolution in the context of mineral associations can provide evidence of how ore deposits formed, or failed to form. Such glimpses of ore-forming process can be recorded by incorporation and release of trace elements from host minerals, the degree of order/disorder in mixed-layer compounds or complex sulfides, or the distribution of nanometer-scale inclusions relative to nanopores or reaction boundaries. Understanding such aspects is paramount in tracking the robustness of mineral geochronometers, equilibrium vs. disequilibrium, mass-transport and mineral reactions in confined spaces. Nano-inclusions in ore minerals can underpin mineral formation and overprinting, or provide insights into the magmatic-to-hydrothermal transition for common ore minerals such as iron-oxides or sulfides, whether these are inherited from pre-existing protoliths, or form from hydrothermal fluids throughout an ore deposit lifespan.

Many new insights have been obtained owing to the expanding development of analytical capability at the nanoscale, including transmission electron microscopy, nanoSIMS, microbeam X-ray absorption spectrometry, and atom probe. In-situ slicing, 3D-tomography, or electron backscatter diffraction on focused-ion-beam-platforms allows unparalleled opportunities to bridge scales of observation on sites of petrogenetic interest. This session invites analytical and experimental studies demonstrating that physicochemical properties observable at the nanoscale represent important clues to elucidate the character and timing of geological processes, including but not limited to magmatic and hydrothermal ore genesis and associated alteration.

The special issue will include papers presented in the session of the same name at Goldschmidt-2018 in Boston (session 06b) but submission is encouraged to all authors wishing to publish new research demonstrating a nanoscale approach to ore-forming processes and similar topics.

Dr. Cristiana L. Ciobanu
Assoc. Prof. Dr. Satoshi Utsunomiya
Prof. Dr. Martin Reich
Assist. Prof. Dr. Oliver Plümper
Guest Editors

Manuscript Submission Information

Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All submissions that pass pre-check are peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Minerals is an international peer-reviewed open access monthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 2400 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Published Papers (12 papers)

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Editorial

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7 pages, 200 KiB

Open AccessEditorial

Editorial for Special Issue “Minerals Down to the Nanoscale: A Glimpse at Ore-Forming Processes”

by Cristiana L. Ciobanu, Satoshi Utsunomiya, Martin Reich, Oliver Plümper and Nigel J. Cook

Minerals 2019, 9(11), 692; https://doi.org/10.3390/min9110692 - 09 Nov 2019

Cited by 2 | Viewed by 2068

Abstract

Minerals form in all types of chemical and physical environments [...] Full article

(This article belongs to the Special Issue Minerals Down to the Nanoscale: A Glimpse at Ore-Forming Processes)

Research

Jump to: Editorial, Other

21 pages, 7388 KiB

Open AccessArticle

Polytypism and Polysomatism in Mixed-Layer Chalcogenides: Characterization of PbBi₄Te₄S₃ and Inferences for Ordered Phases in the Aleksite Series

by Nigel J. Cook, Cristiana L. Ciobanu, Wenyuan Liu, Ashley Slattery, Benjamin P. Wade, Stuart J. Mills and Christopher J. Stanley

Minerals 2019, 9(10), 628; https://doi.org/10.3390/min9100628 - 12 Oct 2019

Cited by 8 | Viewed by 3158

Abstract

Bi-Pb-chalcogenides of the aleksite series represent homologous mixed-layer compounds derived from tetradymite (Bi₂Te₂S). Considering tetradymite as composed of five-atom (Bi₂Te₂S) layers, the named minerals of the aleksite homologous series, aleksite (PbBi₂Te₂S₂) and saddlebackite, (Pb₂Bi₂Te₂S₃) have been considered as phases formed by regular stacking of longer seven- and nine-atom layers. High-angle annular dark-field scanning transmission electron microscope (HAADF-STEM) imaging of thinned foils prepared in-situ on domains deemed homogeneous from electron probe microanalysis, STEM energy-dispersive X-ray spectrometry (EDS) element mapping and fast Fourier transforms (FFTs) from the images offer new insights into these structures. The hitherto-unnamed phase, PbBi₄Te₄S₃, previously interpreted as regular intergrowths of five- and seven-atom layers, is characterized in terms of regular repeats of five- and seven-atom layers over distances of at least 350 nm, defining the (57), or 24H polytype. Imaging of other domains in the same lamella with identical composition at the electron microprobe scale reveals the presence of two additional polytypes: (5559), or 48H; and (557.559) or 72H. Unit cell dimensions for all three polytypes of PbBi₄Te₄S₃ can be both measured and predicted from the HAADF STEM imaging and FFTs. STEM EDS mapping of each polytype confirm the internal structure of each layer. Lead and S occur within the centre of the layers, i.e., Te–Bi–S–Pb–S–Bi–Te in the seven-atom layer, Te–Bi–S–Pb–S–Pb–S–Bi–Te in the nine-atom layer, and so on. Polytypism is an intrinsic feature of the aleksite series, with each named mineral or unnamed phase, except the simple five-atom layer, defined by several alternative stacking sequences of different length, readily explaining the differing c values given in previous work. Homology is defined in terms of layer width and the stacking arrangement of those layers. Coherent structures of the same composition need not only be built of layers of adjacent size (i.e., five- and seven-atom layers) but, as exemplified by the (5559) polytype, may also contain non-adjacent layers, a finding not anticipated in previous work. New polysomes remain to be discovered in nature and each potentially exists as multiple polytypes. The present study further emphasizes the utility of HAADF STEM imaging and atomic-scale STEM EDS element mapping as an optimal tool for tracking stacking sequences and characterising structures in mixed-layer compounds. Full article

(This article belongs to the Special Issue Minerals Down to the Nanoscale: A Glimpse at Ore-Forming Processes)

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26 pages, 28327 KiB

Open AccessArticle

Nanoscale Study of Titanomagnetite from the Panzhihua Layered Intrusion, Southwest China: Multistage Exsolutions Record Ore Formation

by Wenyuan Gao, Cristiana L. Ciobanu, Nigel J. Cook, Ashley Slattery, Fei Huang and Dan Song

Minerals 2019, 9(9), 513; https://doi.org/10.3390/min9090513 - 26 Aug 2019

Cited by 8 | Viewed by 3676

Abstract

Titanomagnetite from Fe-Ti-V ores of the Lanjiahuoshan deposit, Panzhihua layered intrusion, Southwest China, was investigated at the nanoscale. The objectives were to establish the composition of exsolution phases and their mutual relationships in order to evaluate the sequence of exsolution among oxide phases, and assess mechanisms of ore formation during magma emplacement. At the micron-scale, titanomagnetite shows crosscutting sets of exsolutions with ilmenite and Al-Mg-Fe-spinel (pleonaste), as well as overprint, both in terms of phase re-equilibration and remobilization of trace elements. Most complex textures were found in titanomagnetite surrounded by ilmenite and this was selected for high-angle annular dark field scanning transmission electron microscopy (HAADF STEM) imaging and STEM energy-dispersive X-ray spectrometry (EDS) spot analysis and mapping on a thin foil prepared in situ on a focused ion beam scanning electron microscope platform. Titanomagnetite revealed two sequential sets of exsolutions, {111} crosscutting {100}, which are associated with changes in phase speciation and trace element distribution patterns. Qandilite is the dominant spinel phase inside titanomagnetite; magnesioferrite is also identified. In contrast, Fe-poor, Al-rich, Mg-bearing spinel is present within ilmenite outside the grain. Vanadium enrichment in newly-formed magnetite lamellae is clear evidence for trace element remobilization. This V-rich magnetite shows epitaxial relationships with ilmenite at the contact with titanomagnetite. Two-fold super-structuring in ilmenite is evidence for non-redox re-equilibration between titanomagnetite and ilmenite, supporting published experimental data. In contrast, the transformation of cubic Ti-rich spinel into rhombohedral ilmenite imaged at the nanoscale represents the “oxy-exsolution” model of titanomagnetite–ilmenite re-equilibration via formation of a transient ulvöspinel species. Nanoscale disorder is encountered as vacancy layers in Ti-rich spinel, and lower symmetry in the Fe-poor, Al-Mg phase, suggesting that slow cooling rates can preserve small-scale phase equilibration. The cooling history of titanomagnetite ore can be reconstructed as three distinct stages, concordant with published models for the magma plumbing system: equilibrium crystallization of Al-rich, Mg-bearing titanomagnetite from cumulus melts at ~55 km, with initial exsolutions occurring above 800 °C at moderate fO₂ conditions (Stage 1); crosscutting {111} exsolutions resulting in formation of qandilite, attributable to temperature increase due to emplacement of another batch of melt affecting the interstitial cumulus during uplift. Formation of 2-fold superstructure ilmenite + V-rich magnetite exsolution pairs representing non-redox equilibration indicates resetting of the cooling path at this stage (Stage 2); and ilmenite formation from pre-existing Ti-rich spinel and ulvöspinel, illustrative of redox-driven cooling paths at <10 km (Stage 3). HAADF STEM provides direct imaging of atomic arrangements, allowing recognition of processes not recognizable at the micron-scale, and can thus be used to constrain exsolution models during ore formation. Full article

(This article belongs to the Special Issue Minerals Down to the Nanoscale: A Glimpse at Ore-Forming Processes)

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24 pages, 8228 KiB

Open AccessArticle

Invisible Gold in Pyrite from Epithermal, Banded-Iron-Formation-Hosted, and Sedimentary Gold Deposits: Evidence of Hydrothermal Influence

by Yuichi Morishita, Napoleon Q. Hammond, Kazunori Momii, Rimi Konagaya, Yuji Sano, Naoto Takahata and Hirotomo Ueno

Minerals 2019, 9(7), 447; https://doi.org/10.3390/min9070447 - 19 Jul 2019

Cited by 14 | Viewed by 6578

Abstract

“Invisible gold” in pyrite is defined as an Au solid solution of the pyrite lattice, sub-microscopic Au nanoparticles (NPs) in the pyrite, or other chemisorption complexes of Au. Because the relationship between the Au and As concentrations in pyrite could indicate the genesis of the deposit, the purpose of this study is to assess the micro-analytical characteristics of the Au–As relationship in pyrite from epithermal and hydrothermally affected sedimentary Au deposits by secondary ion mass spectrometry. The Au and As concentrations in pyrite vary from 0.04 to 30 ppm and from 1 to 1000 ppm, respectively, in the high-sulfidation Nansatsu-type epithermal deposits; these concentrations are both lower than those of the low-sulfidation epithermal Hishikari deposit. The Au concentrations in pyrrhotite and pyrite reach 6 and 0.3 ppm, respectively, in the Kalahari Goldridge banded-iron-formation-hosted gold deposit, and Au in pyrrhotite may sometimes exist as NPs, whereas As concentrations in pyrrhotite and pyrite are both low and lie in a narrow range from 6 to 22 ppm. Whether Au is present as NPs is important in ore dressing. The Au and As concentrations in pyrite from the Witwatersrand gold field range from 0.02 to 1.1 ppm and from 8 to 4000 ppm, respectively. The shape of the pyrite grains might prove to be an indicator of the hydrothermal influence on deposits of sedimentary origin, which implies the genesis of the deposits. Full article

(This article belongs to the Special Issue Minerals Down to the Nanoscale: A Glimpse at Ore-Forming Processes)

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21 pages, 20415 KiB

Open AccessArticle

Copper-Arsenic Nanoparticles in Hematite: Fingerprinting Fluid-Mineral Interaction

by Max R. Verdugo-Ihl, Cristiana L. Ciobanu, Ashley Slattery, Nigel J. Cook, Kathy Ehrig and Liam Courtney-Davies

Minerals 2019, 9(7), 388; https://doi.org/10.3390/min9070388 - 27 Jun 2019

Cited by 14 | Viewed by 3973

Abstract

Metal nanoparticles (NP) in minerals are an emerging field of research. Development of advanced analytical techniques such as Z-contrast imaging and mapping using high-angle annular dark field scanning transmission electron microscopy (HAADF STEM) allows unparalleled insights at the nanoscale. Moreover, the technique provides a link between micron-scale textures and chemical patterns if the sample is extracted in situ from a location of petrogenetic interest. Here we use HAADF STEM imaging and energy-dispersive X-ray spectrometry (EDX) mapping/spot analysis on focused ion beam prepared foils to characterise atypical Cu-As-zoned and weave-twinned hematite from the Olympic Dam deposit, South Australia. We aim to determine the role of solid-solution versus the presence of discrete included NPs in the observed zoning and to understand Cu-As-enrichment processes. Relative to the grain surface, the Cu-As bands extend in depth as (sub)vertical trails of opposite orientation, with Si-bearing hematite NP inclusions on one side and coarser cavities (up to hundreds of nm) on the other. The latter host Cu and Cu-As NPs, contain mappable K, Cl, and C, and display internal voids with rounded morphologies. Aside from STEM-EDX mapping, the agglomeration of native copper NPs was also assessed by high-resolution imaging. Collectively, such characteristics, corroborated with the geometrical outlines and negative crystal shapes of the cavities, infer that these are opened fluid inclusions with NPs attached to inclusion walls. Hematite along the trails features distinct nanoscale domains with lattice defects (twins, 2-fold superstructuring) relative to hematite outside the trails, indicating this is a nanoprecipitate formed during replacement processes, i.e., coupled dissolution and reprecipitation reactions (CDRR). Transient porosity intrinsically developed during CDRR can trap fluids and metals. Needle-shaped and platelet Cu-As NPs are also observed along (sub)horizontal bands along which Si, Al and K is traceable along the margins. The same signature is depicted along nm-wide planes crosscutting at 60° and offsetting (012)-twins in weave-twinned hematite. High-resolution imaging shows linear and planar defects, kink deformation along the twin planes, misorientation and lattice dilation around duplexes of Si-Al-K-planes. Such defects are evidence of strain, induced during fluid percolation along channels that become wider and host sericite platelets, as well as Cl-K-bearing inclusions, comparable with those from the Cu-As-zoned hematite, although without metal NPs. The Cu-As-bands mapped in hematite correspond to discrete NPs formed during interaction with fluids that changed in composition from alkali-silicic to Cl- and metal-bearing brines, and to fluid rates that evolved from slow infiltration to erratic inflow controlled by fault-valve mechanism pumping. This explains the presence of Cu-As NPs hosted either along Si-Al-K-planes (fluid supersaturation), or in fluid inclusions (phase separation during depressurisation) as well as the common signatures observed in hematite with variable degrees of fluid-mineral interaction. The invoked fluids are typical of hydrolytic alteration and the fluid pumping mechanism is feasible via fault (re)activation. Using a nanoscale approach, we show that fluid-mineral interaction can be fingerprinted at the (atomic) scale at which element exchange occurs. Full article

(This article belongs to the Special Issue Minerals Down to the Nanoscale: A Glimpse at Ore-Forming Processes)

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34 pages, 22416 KiB

Open AccessArticle

Zircon at the Nanoscale Records Metasomatic Processes Leading to Large Magmatic–Hydrothermal Ore Systems

by Liam Courtney-Davies, Cristiana L. Ciobanu, Max R. Verdugo-Ihl, Ashley Slattery, Nigel J. Cook, Marija Dmitrijeva, William Keyser, Benjamin P. Wade, Urs I. Domnick, Kathy Ehrig, Jing Xu and Alkiviadis Kontonikas-Charos

Minerals 2019, 9(6), 364; https://doi.org/10.3390/min9060364 - 16 Jun 2019

Cited by 15 | Viewed by 6252

Abstract

The petrography and geochemistry of zircon offers an exciting opportunity to better understand the genesis of, as well as identify pathfinders for, large magmatic–hydrothermal ore systems. Electron probe microanalysis, laser ablation inductively coupled plasma mass spectrometry, high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) imaging, and energy-dispersive X-ray spectrometry STEM mapping/spot analysis were combined to characterize Proterozoic granitic zircon in the eastern Gawler Craton, South Australia. Granites from the ~1.85 Ga Donington Suite and ~1.6 Ga Hiltaba Suite were selected from locations that are either mineralized or not, with the same style of iron-oxide copper gold (IOCG) mineralization. Although Donington Suite granites are host to mineralization in several prospects, only Hiltaba Suite granites are considered “fertile” in that their emplacement at ~1.6 Ga is associated with generation of one of the best metal-endowed IOCG provinces on Earth. Crystal oscillatory zoning with respect to non-formula elements, notably Fe and Cl, are textural and chemical features preserved in zircon, with no evidence for U or Pb accumulation relating to amorphization effects. Bands with Fe and Ca show mottling with respect to chloro–hydroxy–zircon nanoprecipitates. Lattice defects occur along fractures crosscutting such nanoprecipitates indicating fluid infiltration post-mottling. Lattice stretching and screw dislocations leading to expansion of the zircon structure are the only nanoscale structures attributable to self-induced irradiation damage. These features increase in abundance in zircons from granites hosting IOCG mineralization, including from the world-class Olympic Dam Cu–U–Au–Ag deposit. The nano- to micron-scale features documented reflect interaction between magmatic zircon and corrosive Fe–Cl-bearing fluids in an initial metasomatic event that follows magmatic crystallization and immediately precedes deposition of IOCG mineralization. Quantification of α-decay damage that could relate zircon alteration to the first percolation point in zircon gives ~100 Ma, a time interval that cannot be reconciled with the 2–4 Ma period between magmatic crystallization and onset of hydrothermal fluid flow. Crystal oscillatory zoning and nanoprecipitate mottling in zircon intensify with proximity to mineralization and represent a potential pathfinder to locate fertile granites associated with Cu–Au mineralization. Full article

(This article belongs to the Special Issue Minerals Down to the Nanoscale: A Glimpse at Ore-Forming Processes)

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23 pages, 30987 KiB

Open AccessArticle

Crystals from the Powellite-Scheelite Series at the Nanoscale: A Case Study from the Zhibula Cu Skarn, Gangdese Belt, Tibet

by Jing Xu, Cristiana L. Ciobanu, Nigel J. Cook and Ashley Slattery

Minerals 2019, 9(6), 340; https://doi.org/10.3390/min9060340 - 03 Jun 2019

Cited by 21 | Viewed by 4120

Abstract

Scheelite (CaWO₄) and powellite (CaMoO₄) are isostructural minerals considered as a non-ideal solid solution series. Micron- to nanoscale investigation of a specimen of skarnoid from Zhibula, Gangdese Belt, Tibet, China, was carried out to assess the identity of the phases within a broad scheelite-powellite (Sch-Pow) compositional range, and to place additional constraints on redox changes during ore formation. An electron probe microanalysis shows that Mo-rich domains within complex oscillatory-zoned single crystals, and as thin sliver-like domains, have a compositional range from 20 mol.% to 80 mol.% Pow. These occur within a matrix of unzoned, close-to-end-member scheelite aggregates (87 mol.%–95 mol.% Sch). Laser-ablation inductively coupled plasma mass spectrometry spot analysis and element mapping reveal systematic partitioning behaviour of trace elements in skarn minerals (grossular₅₀, diopside₈₀, anorthite, and retrograde clinozoisite) and scheelite-powellite aggregates. The Mo-rich domains feature higher concentrations of As, Nb, and light rare earth elements LREE, whereas W-rich domains are comparatively enriched in Y and Sr. Transmission electron microscopy (TEM) was carried out on focused-ion-beam-prepared foils extracted in situ from domains with oscillatory zoning occurring as slivers of 20 mol.%–40 mol.% Pow and 48 mol.%–80 mol.% Pow composition within an unzoned low-Mo matrix (20 mol.% Pow). Electron diffractions, high-angular annular dark field (HAADF) scanning-TEM (STEM) imaging, and energy-dispersive spectroscopy STEM mapping show chemical oscillatory zoning with interfaces that have continuity in crystal orientation throughout each defined structure, zoned grain or sliver. Non-linear thermodynamics likely govern the patterning and presence of compositionally and texturally distinct domains, in agreement with a non-ideal solid solution. We show that the sharpest compositional contrasts are also recognisable by variation in growth direction. Atomic-scale resolution imaging and STEM simulation confirm the presence of scheelite-powellite within the analysed range (20 mol.%–80 mol.% Pow). Xenotime-(Y) inclusions occur as nm-wide needles with epitaxial orientation to the host scheelite-powellite matrix throughout both types of patterns, but no discrete Mo- or W-bearing inclusions are observed. The observed geochemical and petrographic features can be reconciled with a redox model involving prograde deposition of a scheelite+molybdenite assemblage (reduced), followed by interaction with low-T fluids, leading to molybdenite dissolution and reprecipitation of Mo as powellite-rich domains (retrograde stage, oxidised). The observation of nanoscale inclusions of xenotime-(Y) within scheelite carries implications for the meaningful interpretation of petrogenesis based on rare earth element (REE) concentrations and fractionation patterns. This research demonstrates that HAADF-STEM is a versatile technique to address issues of solid solution and compositional heterogeneity. Full article

(This article belongs to the Special Issue Minerals Down to the Nanoscale: A Glimpse at Ore-Forming Processes)

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25 pages, 9177 KiB

Open AccessArticle

Detection of Trace Elements/Isotopes in Olympic Dam Copper Concentrates by nanoSIMS

by Mark Rollog, Nigel J. Cook, Paul Guagliardo, Kathy Ehrig, Cristiana L. Ciobanu and Matt Kilburn

Minerals 2019, 9(6), 336; https://doi.org/10.3390/min9060336 - 30 May 2019

Cited by 17 | Viewed by 4403

Abstract

Many analytical techniques for trace element analysis are available to the geochemist and geometallurgist to understand and, ideally, quantify the distribution of trace and minor components in a mineral deposit. Bulk trace element data are useful, but do not provide information regarding specific host minerals—or lack thereof, in cases of surface adherence or fracture fill—for each element. The CAMECA nanoscale secondary ion mass spectrometer (nanoSIMS) 50 and 50L instruments feature ultra-low minimum detection limits (to parts-per-billion) and sub-micron spatial resolution, a combination not found in any other analytical platform. Using ore and copper concentrate samples from the Olympic Dam mining-processing operation, South Australia, we demonstrate the application of nanoSIMS to understand the mineralogical distribution of potential by-product and detrimental elements. Results show previously undetected mineral host assemblages and elemental associations, providing geochemists with insight into mineral formation and elemental remobilization—and metallurgists with critical information necessary for optimizing ore processing techniques. Gold and Te may be seen associated with brannerite, and Ag prefers chalcocite over bornite. Rare earth elements may be found in trace quantities in fluorapatite and fluorite, which may report to final concentrates as entrained liberated or gangue-sulfide composite particles. Selenium, As, and Te reside in sulfides, commonly in association with Pb, Bi, Ag, and Au. Radionuclide daughters of the ²³⁸U decay chain may be located using nanoSIMS, providing critical information on these trace components that is unavailable using other microanalytical techniques. These radionuclides are observed in many minerals but seem particularly enriched in uranium minerals, some phosphates and sulfates, and within high surface area minerals. The nanoSIMS has proven a valuable tool in determining the spatial distribution of trace elements and isotopes in fine-grained copper ore, providing researchers with crucial evidence needed to answer questions of ore formation, ore alteration, and ore processing. Full article

(This article belongs to the Special Issue Minerals Down to the Nanoscale: A Glimpse at Ore-Forming Processes)

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35 pages, 18227 KiB

Open AccessArticle

Silician Magnetite: Si–Fe-Nanoprecipitates and Other Mineral Inclusions in Magnetite from the Olympic Dam Deposit, South Australia

by Cristiana L. Ciobanu, Max R. Verdugo-Ihl, Ashley Slattery, Nigel J. Cook, Kathy Ehrig, Liam Courtney-Davies and Benjamin P. Wade

Minerals 2019, 9(5), 311; https://doi.org/10.3390/min9050311 - 20 May 2019

Cited by 31 | Viewed by 5878

Abstract

A comprehensive nanoscale study on magnetite from samples from the outer, weakly mineralized shell at Olympic Dam, South Australia, has been undertaken using atom-scale resolution High Angle Annular Dark Field Scanning Transmission Electron Microscopy (HAADF STEM) imaging and STEM energy-dispersive X-ray spectrometry mapping and spot analysis, supported by STEM simulations. Silician magnetite within these samples is characterized and the significance of nanoscale inclusions in hydrothermal and magmatic magnetite addressed. Silician magnetite, here containing Si–Fe-nanoprecipitates and a diverse range of nanomineral inclusions [(ferro)actinolite, diopside and epidote but also U-, W-(Mo), Y-As- and As-S-nanoparticles] appears typical for these samples. We observe both silician magnetite nanoprecipitates with spinel-type structures and a γ-Fe_1.5SiO₄ phase with maghemite structure. These are distinct from one another and occur as bleb-like and nm-wide strips along d₁₁₁ in magnetite, respectively. Overprinting of silician magnetite during transition from K-feldspar to sericite is also expressed as abundant lattice-scale defects (twinning, faults) associated with the transformation of nanoprecipitates with spinel structure into maghemite via Fe-vacancy ordering. Such mineral associations are characteristic of early, alkali-calcic alteration in the iron-oxide copper gold (IOCG) system at Olympic Dam. Magmatic magnetite from granite hosting the deposit is quite distinct from silician magnetite and features nanomineral associations of hercynite-ulvöspinel-ilmenite. Silician magnetite has petrogenetic value in defining stages of ore deposit evolution at Olympic Dam and for IOCG systems elsewhere. The new data also add new perspectives into the definition of silician magnetite and its occurrence in ore deposits. Full article

(This article belongs to the Special Issue Minerals Down to the Nanoscale: A Glimpse at Ore-Forming Processes)

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18 pages, 4572 KiB

Open AccessArticle

Nanoscale Structure of Zoned Laurites from the Ojén Ultramafic Massif, Southern Spain

by Sandra Baurier-Aymat, Abigail Jiménez-Franco, Josep Roqué-Rosell, José María González-Jiménez, Fernando Gervilla, Joaquín A. Proenza, Joan Mendoza and Fernando Nieto

Minerals 2019, 9(5), 288; https://doi.org/10.3390/min9050288 - 11 May 2019

Cited by 10 | Viewed by 3247

Abstract

We report the first results of a combined focused ion beam and high-resolution transmission electron microscopy (FIB/HRTEM) investigation of zoned laurite (RuS₂)-erlichmanite (OS₂) in mantle-hosted chromitites. These platinum-group minerals form isolated inclusions (<50 µm across) within larger crystals of unaltered chromite form the Ojén ultramafic massif (southern Spain). High-magnification electron microscopy (HMEM), high angle-annular dark field (HAADF) and precession electron diffraction (PED) data revealed that microscale normal zoning in laurite consisting of Os-poor core and Os-rich rims observed by conventional micro-analytical techniques like field emission scanning electron microscope and electron microprobe analysis (FE-SEM and EPMA) exist at the nanoscale approach in single laurite crystals. At the nanoscale, Os poor cores consist of relatively homogenous pure laurite (RuS₂) lacking defects in the crystal lattice, whereas the Os-richer rim consists of homogenous laurite matrix hosting fringes (10–20 nm thickness) of almost pure erlichmanite (OsS₂). Core-to-rim microscale zoning in laurite reflects a nonequilibrium during laurite crystal growth, which hampered the intra-crystalline diffusion of Os. The origin of zoning in laurite is related to the formation of the chromitites in the Earth’s upper mantle but fast cooling of the chromite-laurite magmatic system associated to fast exhumation of the rocks would prevent the effective dissolution of Os in the laurite even at high temperatures (~1200 °C), allowing the formation/preservation of nanoscale domains of erlichmanite in laurite. Our observation highlights for the first time the importance of nanoscale studies for a better understanding of the genesis of platinum-group minerals in magmatic ore-forming systems. Full article

(This article belongs to the Special Issue Minerals Down to the Nanoscale: A Glimpse at Ore-Forming Processes)

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26 pages, 12713 KiB

Open AccessArticle

Mineralogy of Zirconium in Iron-Oxides: A Micron- to Nanoscale Study of Hematite Ore from Peculiar Knob, South Australia

by William Keyser, Cristiana L. Ciobanu, Nigel J. Cook, Holly Feltus, Geoff Johnson, Ashley Slattery, Benjamin P. Wade and Kathy Ehrig

Minerals 2019, 9(4), 244; https://doi.org/10.3390/min9040244 - 19 Apr 2019

Cited by 9 | Viewed by 4988

Abstract

Zirconium is an element of considerable petrogenetic significance but is rarely found in hematite at concentrations higher than a few parts-per-million (ppm). Coarse-grained hematite ore from the metamorphosed Peculiar Knob iron deposit, South Australia, contains anomalous concentrations of Zr and has been investigated using microanalytical techniques that can bridge the micron- to nanoscales to understand the distribution of Zr in the ore. Hematite displays textures attributable to annealing under conditions of high-grade metamorphism, deformation twins (r~85° to hematite elongation), relict magnetite and fields of sub-micron-wide inclusions of baddeleyite as conjugate needles with orientation at ~110°/70°. Skeletal and granoblastic zircon, containing only a few ppm U, are both present interstitial to hematite. Using laser-ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) spot analysis and mapping, the concentration of Zr in hematite is determined to be ~260 ppm on average (up to 680 ppm). The Zr content is, however, directly attributable to nm-scale inclusions of baddeleyite pervasively distributed throughout the hematite rather than Zr in solid solution. Distinction between nm-scale inclusions and lattice-bound trace element substitutions cannot be made from LA-ICP-MS data alone and requires nanoscale characterization. Scandium-rich (up to 0.18 wt. % Sc₂O₃) cores in zircon are documented by microprobe analysis and mapping. Using high-angle annular dark field scanning transmission electron microscopy imaging (HAADF-STEM) and energy-dispersive spectrometry STEM mapping of foils prepared in-situ by focused ion beam methods, we identify [

0 \bar{1} 1

]_baddeleyite epitaxially intergrown with [

2 \bar{2} .1

]_hematite. Lattice vectors at 84–86° underpinning the epitaxial intergrowth orientation correspond to directions of r-twins but not to the orientation of the needles, which display a ~15° misfit. This is attributable to directions of trellis exsolutions in a precursor titanomagnetite. U–Pb dating of zircon gives a ²⁰⁶Pb/²³⁸U weighted mean age of 1741 ± 49 Ma (sensitive high-resolution ion microprobe U–Pb method). Based on the findings presented here, detrital titanomagnetite from erosion of mafic rocks is considered the most likely source for Zr, Ti, Cr and Sc. Whether such detrital horizons accumulated in a basin with chemical precipitation of Fe-minerals (banded iron formation) is debatable, but such Fe-rich sediments clearly included detrital horizons. Martitization during the diagenesis-supergene enrichment cycle was followed by high-grade metamorphism during the ~1.73–1.69 Ga Kimban Orogeny during which martite recrystallized as granoblastic hematite. Later interaction with hydrothermal fluids associated with ~1.6 Ga Hiltaba-granitoids led to W, Sn and Sb enrichment in the hematite. By reconstructing the evolution of the massive orebody at Peculiar Knob, we show how application of complimentary advanced microanalytical techniques, in-situ and on the same material but at different scales, provides critical constraints on ore-forming processes. Full article

(This article belongs to the Special Issue Minerals Down to the Nanoscale: A Glimpse at Ore-Forming Processes)

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Open AccessTechnical Note

Critical Metal Particles in Copper Sulfides from the Supergiant Río Blanco Porphyry Cu–Mo Deposit, Chile

by Jorge Crespo, Martin Reich, Fernando Barra, Juan José Verdugo and Claudio Martínez

Minerals 2018, 8(11), 519; https://doi.org/10.3390/min8110519 - 09 Nov 2018

Cited by 25 | Viewed by 5403

Abstract

Porphyry copper–molybdenum deposits (PCDs) are the world’s most important source of copper, molybdenum and rhenium. Previous studies have reported that some PCDs can have sub-economic to economic grades of critical metals, i.e., those elements that are both essential for modern societies and subject to the risk of supply restriction (e.g., platinum group elements (PGE), rare earth elements (REE), In, Co, Te, Ge, Ga, among others). Even though some studies have reported measured concentrations of Pd and Pt in PCDs, their occurrence and mineralogical forms remain poorly constrained. Furthermore, these reconnaissance studies have focused predominantly on porphyry Cu–Au deposits, but very limited information is available for porphyry Cu–Mo systems. In this contribution, we report the occurrence of critical metal (Pd, Pt, Au, Ag, and Te) inclusions in copper sulfides from one of the largest PCDs in the world, the supergiant Río Blanco-Los Bronces deposit in central Chile. Field emission scanning electron microscope (FESEM) observations of chalcopyrite and bornite from the potassic alteration zone reveal the presence of micro- to nano-sized particles (<1–10 μm) containing noble metals, most notably Pd, Au, and Ag. The mineralogical data show that these inclusions are mostly tellurides, such as merenskyite ((Pd, Pt) (Bi, Te)₂), Pd-rich hessite (Ag₂Te), sylvanite ((Ag,Au)Te₂) and petzite (Ag₃AuTe₂). The data point to Pd (and probably Pt) partitioning in copper sulfides during the high-temperature potassic alteration stage, opening new avenues of research aimed at investigating not only the mobility of PGE during mineralization and partitioning into sulfides, but also at exploring the occurrence of critical metals in porphyry Cu–Mo deposits. Full article

(This article belongs to the Special Issue Minerals Down to the Nanoscale: A Glimpse at Ore-Forming Processes)

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