Silician Magnetite: Si–Fe-nanoprecipitates and other mineral inclusions in magnetite from the Olympic Dam deposit, South Australia

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

Zircon at the nanoscale records metasomatic processes leading to large magmatic-hydrothermal ore systems

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.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-Charo

Lifting the cloak of invisibility: Gold in pyrite from the Olympic Dam Cu-U-Au-Ag deposit, South Australia

“Invisible gold” refers to gold (Au) occurring either within the lattice of a host sulfide or as discrete nanoparticles (NPs, 50% of pyrites contain measurable Au and As, and plot below the Au-As solubility curve. Au and As are geochemically associated with Te, Bi, Pb, Ag, and Sn. Primary oscillatory zoning patterns in pyrite defined by As-Co-Ni are reshaped by processes of dissolution-reprecipitation, including new nanoscale growth and rhythmical misorientation structures. Low-angle slip dislocations, twist-wall boundaries and deformation-dipole nanostructures are associated with Te-Bi-Pb-enrichment and host Au-Ag-telluride nanoparticles (NPs). Electrum NPs occur associated with pores coated by Bi-Ag-tellurides or within chalcopyrite particles. Bi-Pb-sulfotellurides, petzite, and sylvanite were identified by atomic-scale scanning transmission electron microscopy. The data support trace element (re)mobilization during pyrite deformation at the brittle to ductile transition (0.5–1 kbar, 300–400 °C) during brecciation. Au-NP formation is decoupled from initial As incorporation in pyrite and instead fingerprints formation of strain-induced, chalcogen-enriched nanoscale structures. Pore-attached NPs suggest scavenging of Au by Bi-bearing melts with higher rates of fluid percolation. Similar scenarios are predictable for pyrite-hosted “invisible Au” in pyrite from other deposits that experienced multiple overprints. Unveiling the cloak of invisibility using contemporary micro- to nano-analytical techniques reveals new layers of complexity with respect to the trace/minor element incorporation in mineral matrices and their subsequent release during overprinting.Kathy Ehrig, Cristiana L. Ciobanu, Max R. Verdugo-Ihl, Marija Dmitrijeva, Nigel J. Cook, and Ashley Slatter

Defining IOCG signatures through compositional data analysis: a case study of lithogeochemical zoning from the Olympic Dam deposit, South Australia

The Olympic Dam Cu-U-Au-Ag deposit is dominantly composed of mineralised hematite-breccias and occurs entirely within the Roxby Downs Granite. Multivariate statistical analysis of a large whole-rock, 15 m-interval geochemical dataset (10,565 samples) was undertaken to identify geochemical signatures characteristic of iron-oxide copper gold (IOCG)-style mineralization and constrain the conspicuous lithogeochemical zonation observed at Olympic Dam. Statistical analyses include principal component analysis on centred logratio (clr)-transformed data coupled with hierarchical clustering. Certain groups of elements that can be interpreted in terms of an evolving hydrothermal system relative to host lithologies are derived from data analysis: granitophile (U-W-Sn-Mo); siderophile (Ni-Co); chalcophile (Ag-Bi) and related elements (As-Sb and Au-Te). The distributions of elements within each group are investigated through three vertical cross-sections and are compared with known lithological and Cu-(Fe)-sulphide zonation. Throughout the Olympic Dam Breccia Complex, the IOCG signature is defined by multi-element combinations of the commodity metals Cu, U, Au, and Ag, coupled with a range of trace elements. Overall, the IOCG signature overlaps well with Fe-metasomatism despite mismatch which is likely due to discrete styles of mineralisation found only on the margins of the deposit and also to the presence of mineralised domains within Fe-poor zones. The IOCG signature is composed of two geochemical associations, which exhibit distinct spatial distributions. The first group, Cu-U3O8-Se-S, shows concentric zonation whereas the second group, Au-W-Mo-Sb-As, forms a vertical ∼1800 m deep corridor in the southeastern lobe of the deposit. The specific Au-W-Mo-As-Sb signature could potentially be generic within IOCG systems across the Olympic Cu-Au province and if so, would provide a proxy model for near-mine exploration.Marija Dmitrijeva, Kathy J. Ehrig, Cristiana L. Ciobanu, Nigel J. Cook, Max R. Verdugo-Ihl, Andrew V. Metcalf

Trace element remobilisation from W-Sn-U-Pb zoned hematite: Nanoscale insights into a mineral geochronometer behaviour during interaction with fluids

Preferential removal of W relative to other trace elements from zoned, W–Sn–U–Pb-bearing hematite coupled with disturbance of U–Pb isotope systematics is attributed to pseudomorphic replacement via coupled dissolution reprecipitation reaction (CDRR). This hematite has been studied down to the nanoscale to understand the mechanisms leading to compositional and U/Pb isotope heterogeneity at the grain scale. High-Angle Annular Dark Field Scanning Transmission Electron Microscopy (HAADF STEM) imaging of foils extracted in situ from three locations across the W-rich to W-depleted domains show lattice-scale defects and crystal structure modifications adjacent to twin planes. Secondary sets of twins and associated splays are common, but wider (up to ~100 nm) inclusion trails occur only at the boundary between the W-rich and W-depleted domains. STEM energy-dispersive X-ray mapping reveals W- and Pb-enrichment along 2–3 nm-wide features defining the twin planes; W-bearing nanoparticles occur along the splays. Tungsten and Pb are both present, albeit at low concentrations, within Na–K–Cl-bearing inclusions along the trails. HAADF STEM imaging of hematite reveals modifications relative to ideal crystal structure. A two-fold hematite superstructure (a = b = c = 10.85 Å; α = β = γ = 55.28°) involving oxygen vacancies was constructed and assessed by STEM simulations with a good match to data. This model can account for significant W release during interaction with fluids percolating through twin planes and secondary structures as CDRR progresses from the zoned domain, otherwise apparently undisturbed at the micrometre scale. Lead remobilisation is confirmed here at the nanoscale and is responsible for a disturbance of U/Pb ratios in hematite affected by CDRR. Twin planes can provide pathways for fluid percolation and metal entrapment during post-crystallisation overprinting. The presence of complex twinning can therefore predict potential disturbances of isotope systems in hematite that will affect its performance as a robust geochronometer.Max R. Verdugo-Ihl, Cristiana L. Ciobanu, Nigel J. Cook, Kathy Ehrig, Ashley Slattery and Liam Courtney-Davie

Mineralization-alteration footprints in the Olympic Dam IOCG district, South Australia: The Acropolis prospect

The Acropolis prospect, 20 km southwest from the Olympic Dam Cu-U-Au-Ag deposit, South Australia, is a vein-style magnetite (±apatite ±hematite) system. A whole-rock dataset comprising 4864 core samples from 14 drillholes was analysed using multivariate statistical analyses to understand and identify geochemical signatures of mineralization, as well as the expressions and extents of hydrothermal alteration. Statistical analysis included unsupervised (principal component analysis, hierarchical and k-means clustering) and supervised (random forests) machine learning algorithms. The geology of the Acropolis prospect is presented as a 3D geological model complemented by cross-sections. The results of statistical analyses are overlaid and interpreted relative to the geological model, and encompass a projection of sodic and propylitic alteration as PC3, and mineralization signature as PC1. Although the mineralization footprint of the Acropolis prospect partially overlaps with a Hiltaba Suite granite, it is not centred on the granite body. A distinct ‘magnetite’ signature of Fe-V-Ni-Co is developed in the southwestern part of Acropolis and represents samples containing >60 wt% Fe. In contrast, the ‘hematite’ signature displays an association of REE, W, Sn, Sb, U, Th, Ca and P, and is present throughout the Acropolis prospect with the exception of drillhole ACD5, which is non-mineralized. Interpolated values of Cu (> 200 ppm) indicate an offset from Fe-rich veins, thus supporting a genetic model in which Cu-bearing mineralization overprints Cu-Au-deficient magnetite-dominant veins. The results obtained provide insights into the evolution from magnetite to hematite-dominant IOCG systems and may provide a proxy for exploration of shallow and economically significant IOCG deposits in the eastern Gawler Craton.Marija Dmitrijeva, Cristiana L. Ciobanu, Kathy J. Ehrig, Nigel J. Cook, Andrew V. Metcalfe, Max R. Verdugo-Ihl, Jocelyn McPhi

Hematite geochemistry and geochronology resolve genetic and temporal links among iron-oxide copper gold systems, Olympic Dam district, South Australia

The Wirrda Well and Acropolis prospects, ~25 km south from the Olympic Dam deposit, are among several dozen examples of iron-oxide copper gold (IOCG) mineralisation forming a 600 km-long province in the eastern Gawler Craton, South Australia. IOCG systems across the province differ in terms of host lithology, iron-oxide mineral associations, intensity of brecciation, and grade of Cu-(U)-Au mineralisation. Previous efforts to provide a geochronological framework for mineralisation, and correlate this with igneous activity, were inhibited by a lack of clear crosscutting features (particularly in breccia-hosted systems) and a scarcity of reliable hydrothermal mineral geochronometers. The earliest generation of hematite, characterised by enrichment in U-W-Sn-Mo and previously reported from Olympic Dam, provides confident U-Pb dates and insights into hydrothermal fluid signatures. Similar hematite is recognised from Wirrda Well and Acropolis, allowing direct comparison between the three IOCG systems. Relationships between early, silician (Wirrda Well) and titaniferous (Acropolis) magnetite and U-bearing hematite at the two prospects differ. Inferred martitisation of magnetite at Acropolis has generated zoned hematite with U-W-Mo-enrichment at constant Sn concentration, but with a marked loss of REE + Y (REY) and Ti, whereas at Wirrda Well, single-crystal zoned hematite, resembling that from Olympic Dam, retains high REY and Sn concentrations. Although morphologies, textures and compositions of U-bearing hematite at Olympic Dam, Wirrda Well and Acropolis vary significantly, a common U-Pb (laser ablation-inductively coupled plasma-mass spectrometry) age of ~1590 Ma is obtained from the most reliable data (²⁰⁷Pb/²⁰⁶Pb: 1598.9 ± 6.3 Ma at Wirrda Well and 1590.6 ± 6.5 Ma at Acropolis). The geochemical signatures of iron-oxides from the two prospects share common trends for U, W, Sn, Mo, high field strength and siderophile elements, comparable with signatures of Fe-oxides from the ‘outer shell’ of the Olympic Dam deposit. Given that datable iron-oxides would seem to be ubiquitous phases throughout the eastern Gawler Craton, the commonality in geochemistry and age of U-bearing hematite from the Olympic Dam district is significant, as it provides a single, traceable mineral to compare IOCG systems across the province.Liam Courtney-Davies, Cristiana.L. Ciobanu, Max R. Verdugo-Ihl, Marija Dmitrijeva, Nigel J. Cook, Kathy Ehrig, Benjamin P. Wad

Nanomineralogy of hydrothermal magnetite from Acropolis, South Australia: genetic implications for iron-oxide copper gold mineralization

Magnetite is the dominant Fe-oxide at the Acropolis IOCG prospect, Olympic Dam district, South Australia. Complementary microbeam techniques, including scanning transmission electron microscopy (STEM), are used to characterize titanomagnetite from veins in volcanic rocks and Ti-poor magnetite from a granite body with uplifted position in the volcanic sequence. A temperature of 670 ± 50 °C is estimated for Ti-poor magnetite using XMg-in-magnetite thermometry. Titanomagnetite, typified by Ti-rich trellis lamellae of ilmenite in magnetite, also displays sub-micrometer inclusions forming densely mottled and orbicular subtypes of titanomagnetite with increasing degree of overprinting. STEM analysis shows nanoparticles (NPs) of spinels and TiO2 polymorphs, anatase, and rutile. These vary as dense, finest-scale, monophase-NPs of spinel sensu stricto in Ti-poor magnetite; two-phase, ulvöspinel-hercynite NPs in primary titanomagnetite; and coarser clusters of NPs (hercynite±gahnite+TiO2-polymorphs), in mottled and orbicular subtypes. Nano-thermobarometry using ilmenite-magnetite pairs gives temperatures in the range ~510–570 (±50) °C, with mineral-pair re-equilibration from primary to orbicular titanomagnetite constrained by changes in fO2 from ilmenite-stable to magnetite+hematite-stable conditions. Epitaxial relationships between spinel and Fe-Ti-oxides along trellis lamellae and among phases forming the NPs support exsolution from magnetitess, followed by replacement via mineral-buffered reactions. Lattice-scale intergrowths between ulvöspinel and ilmenite within NPs are interpreted as exsolution recording cooling under O2-conserving conditions, whereas the presence of both TiO2-polymorphs displaying variable order-disorder phenomena is evidence for subtly fO2-buffered reactions from anatase (reducing) to rutile (more oxidizing) stabilities. Transient formation of O-deficient phases is retained during replacement of ilmenite by anatase displaying crystallographic-shear planes. Development of dense inclusion mottling and orbicular textures are associated with NP coarsening and clustering during vein re-opening. Fluid-assisted replacement locally recycles trace elements, forming gahnite NPs or discrete Sc-Ti-phases. Hydrothermal titanomagnetite from Acropolis is comparable with magmatic magnetite in granites across the district and typifies early, alkali-calcic alteration. Open-fracture circulation, inhibiting additional supply of Si, Ca, K, and so on during magnetite precipitation, prohibits formation of silician magnetite hosting calc-silicate NPs, as known from IOCG systems characterized by rock-buffered alteration of host lithologies. Obliteration of trellis textures during subsequent overprinting could explain the scarcity of this type of hydrothermal magnetite in other IOCG systems.Max R. Verdugo-Ihl, Cristiana L. Ciobanu, Nigel J. Cook, Kathy Ehrig, Ashley Slattery, Liam Courtney-Davies and Marija Dmitrijev

Geochemical Data Analysis of Iron Oxide Copper-Gold Mineralization, Wirrda Well Prospect, South Australia

Multivariate statistical analysis encompasses a range of methods that can fingerprint mineralization, alteration, and host-rock signatures within an ore system, thus assisting in interpretation of ore deposit models and supporting exploration programs. We utilize numeric interpolation of metals (Fe, Cu, and U), principal component analysis (PCA), and a Random Forest (RF) classification, applied to whole-rock geochemical data, to define metal distribution patterns and geochemical signatures of alteration/Fe oxide mineralization in the Wirrda Well iron oxide copper-gold (IOCG) prospect. The prospect is located in the Olympic Dam district, Gawler Craton (South Australia), bounded by NW- and NE-trending faults and characterized by two distinct residual gravity anomalies: Wirrda Well North (WW-North) and Wirrda Well South (WW-South). The mineralization is attributed to hydrothermal activity associated with magmatism at -1.6 Ga that generated the Gawler Silicic Large Igneous Province (SLIP), corroborated by U-Pb dates of hematite. The mineralization is hosted by the -1.85 Ga Donington Granitoid Suite and abundant mafic dikes, the majority of which are considered to predate mineralization. Five lithogeochemical clusters are defined from PCA, hierarchical, and k-means clustering, efficiently discriminating least-altered felsic lithologies from altered, mixed lithologies (felsic and mafic) and, importantly, two distinct mineralization clusters, representing magnetite and hematite. The RF method is successfully applied to a larger data set with a smaller number of analyzed elements to extrapolate the results over the whole prospect. WW-North is characterized by an Fe-V-Ni-Co signature defined as "magnetite-type," whereas WW-South contains higher-grade Cu-Au(+/- Bi-Ag) mineralization and has a marked Mo-W-U(+/- Sn) signature defined as "hematite-type." The latter is considered a characteristic hypogene hydrothermal signature in the Olympic Dam District. Sodic and hydrolytic alteration are associated with Fe metasomatism and are depicted by the magnetite and hematite clusters, respectively. In combination, the results indicate that premineralization mafic dikes provided permeable structures for fluid focusing and metal deposition, since metals are concentrated by their contacts with host granite, specifically in WW-North. The metal interpolations and geochemical data analysis suggest strong lithological-structural control on IOCG mineralization at Wirrda Well.Dmitrijeva, M (Dmitrijeva, Marija), Ciobanu, CL (Ciobanu, Cristiana L.), Ehrig, K (Ehrig, Kathy), Cook, NJ (Cook, Nigel J.), Verdugo-Ihl, MR (Verdugo-Ihl, Max R.), Metcalfe, AV (Metcalfe, Andrew, V), Kamenetsky, VS (Kamenetsky, Vadim S.), McPhie, J (McPhie, Jocelyn), Carew, M (Carew, Mick)

Halogens in hydrothermal sphalerite record origin of ore-forming fluids

The halogens Cl and Br are sensitive indicators for the origin of ore-forming fluids. Here, we use a combination of microchemical and microscopic methods to show that measurable concentrations of these elements commonly occur as atomic-scale substitutions in hydrothermal sphalerite. Furthermore, the Cl/Br ratios of halogen-rich sphalerites are indistinguishable from those of the corresponding ore-forming fluids. Thus, they record fluid compositions, which in turn record fluid origin. Given the abundance of sphalerite in hydrothermal base-metal deposits, as well as the relative ease of conducting in situ microchemical analyses, the halogen signature of sphalerite has the potential to become a sensitive proxy to distinguish between different ore-forming environments.Max Frenzel, Nigel J. Cook, Cristiana L. Ciobanu, Ashley D. Slattery, Benjamin P. Wade, Sarah Gilbert, Kathy Ehrig, Mathias Burisch, Max R. Verdugo-Ihl, and Panagiotis Voudouri