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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-Fe1.5SiO4 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.

Abstract:The study of ore minerals is rapidly transforming due to an explosion of new microand nano-analytical technologies. These advanced microbeam techniques can expose the physical and chemical character of ore minerals at ever-better spatial resolution and analytical precision. The insights that can be obtained from ten of today's most important, or emerging, techniques and methodologies are reviewed: laser-ablation inductively-coupled plasma mass spectrometry; focussed ion beam-scanning electron microscopy; high-angle annular dark field scanning transmission electron microscopy; electron back-scatter diffraction; synchrotron X-ray fluorescence mapping; automated mineral analysis (Quantitative Evaluation of Mineralogy via Scanning Electron Microscopy and Mineral Liberation Analysis); nanoscale secondary ion mass spectrometry; atom probe tomography; radioisotope geochronology using ore minerals; and, non-traditional stable isotopes. Many of these technical advances cut across conceptual boundaries between mineralogy and geochemistry and require an in-depth knowledge of the material that is being analysed. These technological advances are accompanied by changing approaches to ore mineralogy: the increased focus on trace element distributions; the challenges offered by nanoscale characterisation; and the recognition of the critical petrogenetic information in gangue minerals, and, thus the need to for a holistic approach to the characterization of mineral assemblages. Using original examples, with an emphasis on iron oxide-copper-gold deposits, we show how increased analytical capabilities, particularly imaging and chemical mapping at the nanoscale, offer the potential to resolve outstanding questions in ore mineralogy. Broad regional or deposit-scale genetic models can be validated or refuted by careful analysis at the smallest scales of observation. As the volume of information at different scales of observation expands, the level of complexity that is revealed will increase, in turn generating additional research questions. Topics that are likely to be a focus of breakthrough research over the coming decades include, understanding atomic-scale distributions of metals and the role of nanoparticles, as well how minerals adapt, at the lattice-scale, to changing physicochemical conditions. Most importantly, the complementary use of advanced microbeam techniques allows for information of different types and levels of quantification on the same materials to be correlated.

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Establishing timescales for iron oxide copper-gold (IOCG) deposit formation and the temporal relationships between ores and the magmatic rocks from which hydrothermal, metal-rich fluids are sourced is often dependent on low-precision data, particularly for deposits that formed during the Proterozoic. Unlike accessory minerals routinely used to track hydrothermal mineralization, iron oxides are dominant components of IOCG systems and are therefore pivotal to understanding deposit evolution. The presence of ubiquitous, magmatic-hydrothermal U-(Pb)-W-Sn-Mo–bearing zoned hematite resolves a range of geochronological issues concerning formation of the ~1.6 Ga Olympic Dam IOCG deposit, South Australia, at up to ~0.05% precision (207Pb/206Pb weighted mean; 2σ) using isotope dilution-thermal ionization mass spectrometry (ID-TIMS). Coupled with chemical abrasion-ID-TIMS zircon dates from host granite and volcanic rocks within and enclosing the ore-body, a confident magmatic-hydrothermal chronology is defined. The youngest zircon date from the granite intrusion hosting Olympic Dam indicates magmatism was occurring up until 1593.28 ± 0.26 Ma. The orebody was principally formed during a major mineralizing event following granite uplift and during cupola collapse, whereby the hematite with the oldest age is recorded in the outer shell of the deposit at 1591.27 ± 0.89 Ma, ~2 m.y. later than the youngest documented magmatic zircon. Hematite dates captured throughout major lithologies, different ore zones, and the ~2-km vertical extent of the deposit support ~2 m.y. of hydrothermal activity. New age constraints on the spatial-temporal evolution of the formation of Olympic Dam are considered with respect to a mantle to crustal continuum model. Cyclical tapping of magma reservoirs to maintain crystal mushes for extended time periods and incremental building of batholiths on the million-year scale prior to main mineralization pulses can explain the ~2-m.y. temporal window temporal window inferred from the data. Despite the challenge of reconciling such an extended window with contemporary models for porphyry deposits (≤1 m.y.), formation of Proterozoic ore deposits has been addressed at high-precision and supports the case that giant IOCG deposits may form over millions of years.

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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.Minerals 2019, 9, 364 3 of 34 followed by partial to complete recrystallization. The amorphous domains begin to interconnect due to the radiation damage (α-decay), over a time period determined by U/Th concentrations and annealing rates [16]. The time dependency of structural damage is highly relevant for geochronology, as it can result in discordance of the U-Pb system, most commonly through Pb-loss. Disturbances to zircon U-Pb systematics via metamictization can, however, be selectively eliminated by chemical abrasion of damaged zones, prior to ID-TIMS, permitting high-precisio...