Search

“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.

The Mount Weld rare earth element (REE) deposit, Western Australia, is one of the largest of its type on Earth. Current mining exploits the high-grade weathered goethite-bearing resource that lies above, and which represents the weathering product of a subjacent carbonatite. The mineralogy, petrography, deportment of lanthanides among the different components, and variation in mineral speciation, textures, and chemistry are examined. Microanalysis, involving scanning electron microscope (SEM) imaging, electron probe microanalysis (EPMA) and laser ablation inductively coupled-plasma mass spectrometry (LA-ICP-MS), was conducted on sized fractions of three crushed and ground laterite ore samples from current and planned production, and a representative sample from the underlying carbonatite. High-magnification imaging of particles in laterite samples show that individual REE-bearing phases are fine-grained and extend in size well below the micron-scale. Nanoscale inclusions of REE-phosphates are observed in apatite, Fe-(Mn)-(hydr)oxides, and quartz, among others. These have the appearance, particularly in fluorapatite, of pervasive, ultrafine dusty domains. Apart from the discrete REE minerals and abundant nano- to micron-scale inclusions in gangue, all ore components analysed by LA-ICP-MS contain trace to minor levels of REEs within their structures. This includes apatite, where low levels of REE are confirmed in preserved igneous apatite, but also Fe- and Mn-(hydr)oxides in which concentrations of hundreds, even thousands of ppm are measured. This is significant given that Fe-(Mn)-(hydr)oxides are the most abundant component of the laterite and points to extensive mobility and redistribution of REEs, and especially HREE, during progressive lateritisation. Late-formed minerals, notably tiny grains of cerianite, reflect a shift to oxidising conditions. REE-fluorocarbonates are the main host for REEs in carbonatite and are systematically replaced by hydrated, Ca-bearing REE-phosphates (largely rhabdophane). The latter displays varied compositions but is characteristically enriched in HREE relative to monazite in the same sample. Fine-grained, compositionally heterogeneous rhabdophane is accompanied by minor amounts of other paragenetically late, hydrated phosphates with enhanced MREE/HREE relative to LREE (although still LREE-dominant). Minor, relict xenotime and zircon are significant HREE carriers. Ilmenite and pyrochlore group members contain REE but contribute only negligibly to the overall REE budget. Although the proportions of individual mineral species differ, the chemistry of key ore components are similar in different laterite samples from the current resource. Mineral signatures are, however, subtly different in the lower grade southeastern part of the deposit, including higher concentrations of HREE relative to LREE in monazite, rhabdophane, florencite and Fe-(Mn)-(hydr)oxides.

Silician magnetite within ~1.85 Ga lithologies hosting the ~1.6 Ga Wirrda Well iron oxide copper gold (IOCG) prospect, South Australia, was examined at the nanoscale. The magnetite is oscillatory-zoned with respect to the density and orientation of nanometer-scale inclusions, among which Si-Fe-nanorods and Al-rich amphibole (as much as hundreds of nanometers long and tens of nanometers wide) form swarms along directions in magnetite. The amphibole is identified as ferro-tschermakite (Ftsk) with the crystal-chemical formula: A(K0.06Na0.01)0.07B(Ca1.65Na0.35)2C(Fe2.072+Al1.64Mg1.15Ti0.06Fe0.043+Mn0.04)5T(Si6.48Al1.52)8O22W(OH)2. This contains single and double rows of a triple-chain silicate attributed to clinojimthompsonite (Cjt) as coherently intergrown (010) zippers along the entire length of the grains. High-angle annular dark-field scanning transmission electron microscopy (HAADF STEM) imaging and simulation of Ftsk and Cjt on the [001] zone axis provide direct visualization of crystal structures. These are defined by the 7- and 10-atom octahedron strips (B+C sites) and flanked by double- and triple-pairs of Si atoms (T sites). Remarkably, the sites for light cations and/or vacancies are clearly imaged as single and double, darkest, diamond-shaped motifs separating the octahedron strips showing that A cavities known in amphibole are readily depicted in the wider-chain silicate. I-beam models show that nanoscale intergrowths among the two silicates are coherent along zigzag chains of cations at the edges of the octahedron strips, with single and double rows of the triple-chain silicate corresponding to 1 and 1.5 unit cells of Cjt (27 and 41 Å intervals along the b axis). This type of polysomatic chain-width disorder is widely reported in Mg-rich pyriboles but is shown here in an Al-Fe-rich amphibole. The lack of planar defects and/or reaction fronts at mutual contacts between three-chain zippers and host amphibole indicates primary co-crystallization growth, promoted by the formation of the Si-Fe-nanorods. Co-crystallizing plagioclase is also preserved in close vicinity to the amphibole hosted by magnetite (from a few nanometers to micrometers apart). In contrast, the replacement of amphibole by phyllosilicates is recognizable as irregular swells along the (010) zippers and results in extensive chloritization of the amphibole during an overprinting event. Pressures of ~11.5 kbar are estimated using Al-in-hornblende nano-geobarometry and calculated Al content in Ftsk (3.16 apfu). Assuming the amphibole-plagioclase association buffered by host magnetite fulfills the textural equilibration criteria required for application of this barometer, we interpret the Ftsk nanoinclusions in magnetite as preserved evidence for amphibolite facies metamorphism affecting host lithologies at Wirrda Well with subsequent retrograde alteration during the ~1.6 Ga IOCG mineralizing event. Magnetite records petrogenetic processes by accommodating variable ranges of nanomineral inclusions and preserving them over geological time scales. HAADF STEM imaging is ideally suited to the depiction of crystal-structural modularity and also provides insights into the evolution of geological terranes with protracted histories.

The accelerated pace of transition to green energy technologies has led to increased demand for rare-earth elements (REEs). Fluorocarbonates from the bastnäsite [REE(CO3)F]—synchysite [CaREE(CO3)2F] group are abundant in nature and the dominant REE minerals in the >10 billion ton Olympic Dam Cu–U–Au–Ag deposit, South Australia. Intergrowths of bastnäsite and synchysite slabs at the nanometer to micron scales are the rule rather than the exception and account for structural and compositional changes between the two endmembers. This article reviews REE-fluorocarbonate mineralogy at Olympic Dam with emphasis on the significance of intergrowths among bastnäsite and synchysite for achievement of thermodynamic equilibrium. Imaging by high-angle annular dark-field scanning transmission electron microscopy (HAADF STEM) allows visualization of atomic-scale periodicity and structural modularity in REE fluorocarbonates and, in turn, determination of domain compositions, which are otherwise below the spatial resolution of microbeam methods. Despite highly irregular, such domains featuring atomic-scale intergrowths can approach the compositions of the next intermediate member phase within each host, implying formation in a system close to thermodynamic equilibrium. Graphic Abstract

Tin-bearing magnetite is reported from several types of magmatic-hydrothermal ore deposits. The question of whether tin is incorporated within solid solution, as Sn4+, or as nanoinclusions remains open, however. We report a micron- to nanoscale investigation of Sn (Mg, Si)-bearing magnetite from serpentinite in the Dulong Zn-Sn-In skarn, South China, with the dual aims of understanding the mechanisms involved in accommodating Sn and associated elements into the Fe-oxide, and the inferences that this carries for constraining the early stages of skarn formation. Magnetite preserves a range of textures that record the evolution of metasomatism during prograde growth of grain cores and retrograde rim replacement. Observations reveal the presence of chondrodite and sellaite (MgF2) as nanoscale inclusions preserved in magnetite. This implies initiation of the Dulong mineralizing system during a humite-bearing, magnesium skarn stage. Magnesium-Si defects, forming along (110) planes prior to Sn-enrichment, are recognized for the first time. Release of high volatile, F-rich fluids is interpreted to lead to precipitation of cassiterite inclusions along directions in magnetite.

Texturally complex minerals can provide critical information on dynamic hydrothermal processes. This study combines cathodoluminescence (CL), laser ablation-inductively coupled plasma-mass spectrometry (LA–ICP–MS), and high-resolution femtosecond laser ablation multi-collector inductively coupled plasma mass spectrometry (fs–LA–MC–ICP–MS) analyses to document textures, in situ Sr-Nd isotope systematics, and trace element compositions of texturally complex scheelite from the Yangjiashan W deposit, South China. The major motivation for this contribution was to reveal the correlation between CL response, textures, and trace element concentrations; document the origin of various REE fractionation patterns; and characterize grain-scale in situ variability of Sr-Nd isotopes of scheelite. Five sub-types of scheelite from both stages, including Sch1 and Sch2 from Stage 1, and Sch3 to Sch5 from Stage 2, are identified. CL images feature complex oscillatory, patchy, and evidence for coupled dissolution-reprecipitation reaction. These scheelites precipitated from reduced fluids and are close to end-member in composition, with Mo concentrations below 46 ppm. Concentrations of other elements vary, e.g., Sr (36–1025 ppm), Nd (8–351 ppm), and Na (7–300 ppm). LA–ICP–MS element maps reveal a large variability in REE concentrations among oscillatory zones and no consistent behavior between REE, Sr and Mo concentration, and CL intensity. Four distinct chondrite-normalized REE fractionation patterns are recognized: LREE-enriched, MREE-enriched, HREE-enriched, and flat patterns. Complex Eu anomalies (δEu = 0.2 to 20.7) are recognized among the five sub-types and are commonly observed within individual grains. Fluid compositions, different substitution mechanisms (i.e., Ca2+ + W6+ = REE3+ + Nb5+, and 2Ca2+ = REE3+ + Na+, 3Ca2+ = 2REE3++ ☐Ca, where ☐Ca is a Ca-site vacancy), primary-secondary processes (i.e., oscillatory and dissolution-reprecipitation, respectively), all contribute to the variation in REE fractionation patterns. Local fluctuation in fluid pH is responsible for the complex Eu anomalies. In situ Sr and Nd isotope signatures for the five sub-types of scheelite show relatively large ranges, i.e., the initial 87Sr/86Sr ratios range from 0.71336 to 0.72617, and the initial εNd values ranging from –24.9 to –7.7, suggesting a source derived from a mixture of magmatic-hydrothermal fluids and the Neoproterozoic slate. Decreasing 87Sr/86Sr ratios from Sch2 to Sch5 record decreasing fluid-rock interaction intensity. Large variation of εNd(t) values (–24.9 to –7.7) of scheelite with oscillatory zoning textures may relate to changes of Sm/Nd ratio of scheelite and contamination from wall rock with inhomogeneous Nd isotope composition. This study highlights the importance of performing coupled LA–ICP–MS mapping and in situ Sr-Nd isotope analyses on sample material that has been characterized in detail at the micrometer scale.

Yuhengtang is a representative slate-hosted Au deposit in the Jiangnan orogenic belt, South China, with a reserve of ~55 t Au and an average grade of ~3.9 g/t. Gold mineralization is characterized by veinlet and disseminated ores comprising native gold, auriferous pyrite, and arsenopyrite. Paragenesis of the Yuhengtang deposit can be divided into three stages. Pre-ore stage 1 is composed of bedding-parallel layers of pyrite in slate of the Neoproterozoic Banxi Group. Main ore stage 2 represents the Au mineralization stage, and two distinct types of mineralization can be distinguished: visible Au-arsenopyrite-pyrite in quartz veinlets and auriferous arsenopyrite-pyrite disseminated within altered slate. Post-ore stage 3 consists of quartz-pyrite-calcite-ankerite veins. In this study, we integrate electron microprobe, laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) and high-resolution ion microprobe (SHRIMP) analyses to document textural, isotopic, and compositional variation among texturally complex pyrite and arsenopyrite assemblages in veinlet and disseminated ores. Additionally, LA-ICP-MS sulfur isotope mapping of pyrite highlights the covariation behavior between trace elements and sulfur isotopes at the grain scale, thus allowing the factors controlling sulfur isotope fractionation in hydrothermal Au deposits to be constrained. Pyrite, of sedimentary origin (stage 1), hosts negligible Au ( All results support that multiple depositional mechanisms within a dynamic mineral system were responsible for Au concentration and define the specific textural, compositional, and sulfur isotope signatures of sulfides in coexisting vein/veinlet and disseminated mineralization. The new data highlight the ore-forming processes-based interpretation for ore genesis and underpin the importance of performing complementary in situ mineralogical analyses to elucidate the source and evolution of ore-forming fluids and enable correct interpretation of the architecture of the hydrothermal Au system.

Ancient metamorphic processes are recorded by the formation of metallic-Pb nanospheres in zircon, a product of internal Pb mobilisation and thermally driven concentration. Here, metallic-Pb nanospheres formed within an ore deposit are characterised for the first time using high-angle annular dark field scanning transmission electron microscopy and energy-dispersive X-ray spectroscopy element-distribution mapping. Exceptional examples from the migmatite-hosted Archean–Paleoproterozoic Challenger Au deposit (Central Gawler Craton, South Australia) support widespread metallic-Pb nanosphere formation in zircon from rocks experiencing granulite-facies metamorphism. We also report new trace-element associations found with metallic-Pb nanospheres and a new mode of occurrence, in which Sc ‘haloes’ form adjacent to metallic-Pb nanospheres within the crystalline zircon lattice. This differs to previously characterised examples of metallic-Pb nanospheres associated with amorphous Si-rich glasses and unidentified Al–Ti, or Fe-bearing phases. Multiple modes of metallic-Pb nanosphere occurrences and trace-element associations suggests multiple modes of formation, probably dependant on zircon composition and metamorphic conditions. Identification of metallic-Pb nanospheres in a growing range of geological settings further highlights the mobility of Pb in zircon and the importance of detailed, nanoscale mineral characterisation, in order to constrain accurate geochronological histories for rocks within high-temperature geological environments.

Hematite (α-Fe2O3) and magnetite (Fe3O4) readily accommodate a wide range of minor and trace elements from across the periodic table at up to wt.% concentrations. This prompts the question of whether these common minerals can also host rare earth elements (lanthanides, Y and Sc; REEs)? If so, what is the chemical and physical nature of the elements: are they incorporated into the oxide crystal structures, or do they occur as nanometer-to micron-sized inclusions of discrete REE-minerals? By combining micron-scale petrography and analysis by LA-ICP-MS with nanoscale imaging and energy-dispersive spectroscopy, the relationships between REEs and iron-oxides are addressed in samples from the world-class Olympic Dam Cu-U-Au-Ag deposit, South Australia. Spatially co-existing silician magnetite and hematite from the outer shell at Olympic Dam show stages of interconversion during which REEs are redistributed. REEs are shown to be preferentially incorporated into the magnetite structure, whereas hematite concentrates U, W, and Sn, and contains negligible structurally bound REEs. Abundant, in-situ NP formation to an abundance of monazite reflects successive overprinting events and remobilization of elements from solid-solution and subsequent trapping as NPs via coupled dissolution replacement reaction. REE-minerals such as florencite can host nanoinclusions of hematite. Atomic-scale observations, including defects in magnetite and an O-deficient, two-fold hematite superstructure show crystal structural accommodation during Fe-oxide interconversion and inclusion nucleation. Both silician magnetite and hematite show nanoscale muscovite forming along planar defects. Understanding the mineralogical deportment of REEs at Olympic Dam carries potential implications for investigating the viability of REE extraction opportunities from any resource in which Fe-oxides are the dominant component.

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, ulvöspinelhercynite 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.

Characterizing the chemical state and physical disposition of uranium that has persisted over geologic time scales is key for modeling the long-term geologic sequestration of nuclear waste, accurate uranium-lead dating, and the use of uranium isotopes as paleo redox proxies. X-ray absorption spectroscopy coupled with molecular dynamics modeling demonstrated that pentavalent uranium is incorporated in the structure of 1.6 billion year old hematite (α-Fe

Trace/minor element variation in pyrite is a feature that has proved invaluable for reconstructing a wide range of geological processes. Routine reflectance observations commonly fail to constrain this variation due to the typically subtle and barely perceptible change in reflectance brought about by deviation from ideal stoichiometry. Such differences may be difficult or impossible to observe in conventional polished sections using standard optical microscopes, at least without oil immersion. Chemical etching and staining, although widely used, are destructive, hazardous, or both, and the etching process is not completely reproducible. Here we use the g correction method to enhance optical digital signal differences obtained in reflected light to constrain compositional heterogeneity in pyrite from a representative hydrothermal ore deposit in eastern China. The g-enhanced images show significant reflectance variation caused by compositional heterogeneity, confirmed by quantitative electron microprobe analysis and qualitative imaging. Higher reflectance domains in g-enhanced images correspond to increases in the effective number of free electrons, whereas darker domains are attributed to the decrease of these free electrons by trace/minor element substitution in pyrite (e.g., As). Gamma correction provides a rapid, effective, non-destructive method to constrain compositional heterogeneity of pyrite through enhancement of reflectance variation. Used alone, this method is unable to determine the chemical composition due to simultaneous substitutions, causing a disparate increase or decrease of reflectance, in most ore minerals. Nevertheless, γ correction may be sufficient to predict the substitution of trace/minor elements under the optical microscope prior to scanning electron microscope imaging and quantitative investigation of mineral composition and may help constrain links between textures and compositions of pyrite in evolving ore systems, which could also be applied to other ore minerals with negligible bireflectance.

Micrometer- to submicrometer-scale indium-rich domains are preserved within sphalerite included in hornfels-hosted pyrrhotite from the Dulong polymetallic skarn, Yunnan, China. The nano-mineralogy of the ZnS-bearing blebs was investigated using scanning transmission electron microscopy on thinned foils extracted in situ from pyrrhotite. Indium incorporation in sphalerite occurs via the coupled substitution 2Zn2+ ↔ Cu+ + In3+; the results thus allow insights into phase relationships in the system ZnS-CuInS2 in which solubility limits are debated with respect to a cubic to tetragonal phase transition. The highest concentrations of In are measured in basket-weave domains from the smallest ZnS blebs or from un-patterned areas in coarser, irregular ZnS inclusions in pyrrhotite. Indium-rich domains contain 17–49 mol% CuInS2, whereas In-poor sphalerite contains

Pyrite commonly incorporates a wide range of trace and minor elements, which in turn may modify some of the mineral’s physical and chemical properties. Published band position data for the Raman spectra of pyrite show a wide variation, and the relationship between band position and the trace/minor element incorporation in pyrite is poorly constrained until now. This prompted a case study on pyrite with varying As content from the Shizilishan Sr-(Pb-Zn) deposit, eastern China, combining electron probe microanalysis with Raman spectroscopy. Results show a significant correlation, with a major downshift (~10 cm–1) of the positions of all three Raman bands with increase of As content from below 0.05 to 4.89 wt % in pyrite. This phenomenon is attributed to increased bond lengths and local distortions within an expanded pyrite crystal structure. Results highlight the potential that Raman spectroscopy offers to estimate the contents of trace/minor elements—especially As—in pyrite. Given that substitution of As into pyrite often facilitates co-incorporation of both economically useful (Au) and environmentally significant elements (Hg and Tl), Raman methodology could provide valuable, rapid assessment of pyrite chemistry in both gold deposit exploration and environmental science, although the impact of laser heating and mechanical polishing needs to be avoided or effectively reduced. Raman spectroscopy may also find a valuable future role within semiautomated multispectral analytical platforms that can generate close- to-real-time geologic information on freshly drilled core directly at the drill site or in outcrop.

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.

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.

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.

Economic interest in indium (In) and other critical metals has accelerated efforts to understand how such elements occur in nature and the controls on their mineralogy. In this contribution, the distribution of In and other trace elements in the Dulong Zn–Sn–In deposit, China, is described, using a holistic approach which targets not only sulfides but also the potential for In and Sn within co-existing oxides and skarn silicates. Sphalerite is the most significant In carrier. Four distinct types of sphalerite are identified, which differ with respect to ore texture and the concentration of In (0.74–4572 ppm). Subordinate amounts of In also occur within chalcopyrite and within andradite garnet, an abundant mineral in the skarn at Dulong and possibly accounting for a significant proportion of total In. Tin is not especially concentrated in either sphalerite or chalcopyrite, occurring instead as cassiterite but with measurable concentrations also in magnetite and skarn silicates. The study confirms that the dominant substitution for In in sphalerite is 2Zn2+ ↔ Cu+ + In3+ but that Ag and Sn may also play a subordinate role in some sphalerite sub-types via the substitution: 3Zn2+ ↔ Ag+ + Sn2+ + In3+. The study highlights that concentrations of In in sphalerite are likely to be heterogeneous at scales from single mineral grains to that of the deposit. The observed partitioning of both In and Sn into skarn silicates, and to a lesser extent, oxides, is a critical factor that may significantly compromise estimations of by-product elements that would be economically recoverable during exploitation of sulfide ores.

The Pefka Cu-Au-Te-In-Se and nearby St Philippos Pb-Zn-Bi-Sn-Ge-Ga-In vein- and breccia-type deposits in western Thrace, Greece, display strong similarities, but also differences in terms of mineralization style, ore mineralogy, and chemistry, and host rock compositions. The Pefka mineralization consists of two crosscutting vein systems with high sulfidation (HS)- and intermediate-sulfidation (IS) assemblages hosted by andesitic lavas and is unusually enriched in In (up to 700 ppm), Te (>1000 ppm), Se (>100 ppm), and Cu (>1 wt%). The main In-carriers are roquesite (CuInS2) and In-bearing “tennantite-(Cu)” and Cu-rich “tennantite-(In)” which contains up to 6.5 wt% In, substituting into the C site. Roquesite is associated with enargite and arsenosulvanite/colusite, as part of the HS assemblage at Pefka. Selenium-bearing galena and a large suite of tellurides including calaverite, sylvanite, petzite, hessite, kostovite, empressite, tellurantimony, and coloradoite, in addition to native tellurium, account for the marked tellurium and selenium enrichment in the ores from Pefka. Tellurides and native gold at Pefka accompany the precipitation of Te-bearing minerals of the tetrahedrite group, such as “stibiogoldfieldite” and “arsenogoldfieldite”, and Cu-excess varieties of tetrahedrite and tennantite. However, the bulk of telluride deposition is associated with normal, fully substituted tetrahedrite-tennantite varieties. The St Philippos deposit is associated with a brecciated fault zone hosted by Eocene sandstones and Oligocene quartz-feldspar porphyry dikes. It is enriched in a large suite of incompatible elements, including Bi (>2000 ppm), Sn (>100 ppm), U (up to 200 ppm), Pb (>1 wt%), Zn (>1 wt%), Mo (up to 62 ppm), Ge (>100 ppm), Ga (up to 466 ppm) and In (up to 222 ppm), contrasting with the element suite defining the nearby Pefka deposit. The main carrier of In, Ga, and Ge is sphalerite (and wurtzite) with In-rich zones in sphalerite containing up to 6.1. wt% In. Germanium and Ga in sphalerite reach concentrations of up to 0.27 and 0.32 wt%, respectively. Sphalerite from the St Philippos deposit is extremely Fe-poor (300 °C) and HS fluid conditions, followed by IS assemblages as temperatures waned. Rhyolitic oxidized magmas are considered to be the sources of metals in the St Philippos deposit; however, their anomalous W, Sn, U, and Bi contents suggest a contamination by crustal rocks. The Cu-Au-Te signature of the Pefka deposit is compatible with a genetic relationship to less fractionated andesitic magmas, although a possible contribution of In from rhyolitic magmas could explain the high In contents of the ore. However, other factors, as for example different metal-deposition mechanisms resulting in metal zonation around causative porphyry centers at depth, may also account for the observed metal endowment in these two deposits. The Sn-Te-In-(Ge-Ga) element association at Pefka and St Philippos is unusual in that it has been previously reported from only a few other places in the world (e.g., Capillitas deposit, Argentina, and the Kawazu deposit, Japan). We conclude based on this exotic mineralization-style that the northeastern part of Greece represents an area of great potential for the exploitation of critical metals and metalloids.

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 R3¯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.

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 Bi2kTe3 (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.

Aluminum-phosphate-sulfate (APS) minerals of the alunite supergroup are minor components of uranium-bearing copper ores from the Olympic Dam deposit, South Australia. They typically represent a family of paragenetically late replacement phases after pre-existing REE-bearing phosphates (fluorapatite, monazite, and xenotime). Characterization with respect to textures and composition allows two groups to be distinguished: Ca-Sr-dominant APS minerals that fall within the woodhouseite and svanbergite compositional fields; and a second REE- and phosphate-dominant group closer to florencite in composition. All phases nevertheless display extensive solid solution among end-members in the broader APS clan and show extensive compositional zoning at the grain-scale. Samples representative of the deposit (flotation concentrate and tailings), as well as those that have been chemically altered during the processing cycle (acid leached concentrate), were studied for comparison. NanoSIMS isotope mapping provides evidence that the APS minerals preferentially scavenge and incorporate daughter radionuclides of the 238U decay chain, notably 226Ra and 210Pb, both over geological time within the deposit and during ore processing. These data highlight the role played by minor phases as hosts for geologically mobile deleterious components in ores as well as during mineral processing. Moreover, Sr-Ca-dominant APS minerals exhibit preferential sorption of Pb from fluid sources, in the form of both common Pb and 210Pb, for the first time revealing potential pathways for 210Pb elimination and reduction from ore processing streams.

The Acropolis prospect is a vein-style magnetite (±apatite ±hematite) system located ~20 km southwest from the giant Olympic Dam iron-oxide copper gold (IOCG) deposit, South Australia. A whole rock...

The IOCG deposit at Olympic Dam (South Australia) is hosted within the Roxby Downs Granite, which displays a weakly mineralised contact to the orebody (hereafter ‘outer shell’). In a mineralogical-geochemical characterisation of Fe-oxides from the outer shell, we show silician magnetite (Si-magnetite) and HFSE-bearing hematite define the early stages of alkali-calcic alteration. This association forms in the presence of hydrothermal K-feldspar and calc-silicates via overprinting of magmatic magnetite and ilmenite breakdown. Geochemical modelling, at ≥ 400 °C, shows such reactions occur at pH-fO2 conditions coinciding with shifts from K-feldspar to sericite, and ilmenite to rutile stability. The subsequent Si-magnetite+siderite association forms down-T in the absence of K-feldspar. Transition from granular to bladed morphologies in Si-magnetite is part of a series of Fe-oxide interconversions, followed by formation of zoned, U-W-Sn-Mo-bearing hematite. Enrichment in REE, Y and U in Si-magnetite and the prevalence of U-W-Sn-Mo-bearing hematite support a granite-derived fluid. Combined, petrographic and geochemical evidence show a transition among Fe-oxides from the outer shell to the orebody attributable to the evolution of the same fluid. Unusual massive magnetite intervals and Fe-oxide nodules in granite are considered due to either the presence of inherited lithologies, metasomatic products, or the result of magnetite-rich, crystal mush forming in the melt. We propose a model, corroborated by recently published data including high-precision U-Pb dating of magmatic zircon and hydrothermal hematite, in which an ‘outer shell’ is initiated at the 6–8 km depth of granite emplacement during volatile release from fluids ponding at intrusion margins. Granite cupola collapse at shallower levels (2–3 km?) follows via uplift along faults, facilitating intense brecciation and ore formation.

Hematite (α-Fe2O3) is a common iron-oxide mineral known to incorporate U into its crystal lattice at up to wt% concentrations and has been previously used to date ore formation within iron-oxide copper gold and banded iron formation deposits. However, there has been no detailed evaluation of the potential challenges this novel mineral geochronometer may present for accurate temporal interpretation. We report a multi-technique U Pb geochronological study comprising laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS), sensitive high-resolution ion microprobe (SHRIMP) and the first isotope dilution-thermal ionization mass spectrometry (ID-TIMS) procedure and analyses using an in-situ grain micro-sampling technique. We assess intra- and inter-sample data reproducibility, and examine the compatibility of spatial and analytical resolutions to texturally and compositionally diverse samples. Five samples of hydrothermal, primary, oscillatory-zoned hematite were analysed from distinct lithologies throughout the ~1.59 Ga Olympic Dam Cu-U-Au-Ag deposit, with typical U concentrations ranging between ~20 and 1000 ppm. LA-ICP-MS mapping of isotope distributions across mm-sized grains allows pinpointing of U-rich and relatively U/Pb isotopically ‘homogeneous’ domains. Micro-domains were extracted via laser-cut square shaped trenches (100 × 100 μm). U Pb datum range in complexity, with concordant age domains measured by ID-TIMS indicating that hematite can retain a near-closed U Pb system over ~1.6 Ga, while also demonstrating that younger Pb-loss events may be recorded. Significant reverse discordance is common in the data, likely to be a real feature due to both internal decoupling and mobility of Pb within a single grain and U Pb fractionation during microbeam analysis. These effects will obscure the interpretation of real ages for Proterozoic samples where non-zero age Pb-loss events occur, and restricts the evaluation of common Pb mixing components. As a result, microbeam analyses may be biased younger or older in terms of 207Pb/206Pb dates in samples with complex histories. Microbeam datum compare favourably with high precision ID-TIMS ages. Although reproducible ID-TIMS U Pb dates were generally not obtained, in the best-case example, a 207Pb/206Pb weighted mean age of 1589.91 ± 0.91 Ma (MSWD = 1.3, n = 5), within 0.2% of the Olympic Dam granite host rock age (1593.87 ± 0.21 Ma) was generated. All five hematite samples dated by LA-ICP-MS and SHRIMP yield weighted mean 207Pb/206Pb dates within 2% of the host granite age after small degrees of data rejection. The results demonstrate that with careful sample petrography, screening and data interpretation, hematite can be considered a very useful U Pb mineral geochronometer, with potential application to all U-bearing Fe-oxide rich mineral systems.

Baryte is a common gangue mineral in many ore systems. Here, we report on a study of baryte chemistry in samples of ore and processing materials (flotation feed, flotation concentrate, flotation tailings, concentrate leach discharge, and tailings leach discharge) from the Olympic Dam Cu-U-Au-Ag deposit, South Australia. Elements that commonly substitute for Ba in the baryte lattice, including Sr and Ca, are measured in variable concentrations reflecting grain-scale zonation and heterogeneity at the scale of the deposit but appear unaffected during processing. Variation in the concentration of some other elements, notably Cu, reflect both the heterogeneous nature of flotation feed and the intimately intergrown character of the sulfide-sulfate assemblage. Measured Pb concentrations in baryte progressively increase during processing from flotation feed to flotation concentrate, and particularly in concentrate leach discharge. Such data suggest that, during sulfuric acid leaching, baryte contained within the concentrate is able to incorporate quantities of Pb that have been mobilized during break-down of Pb-bearing minerals (notably U-minerals containing radiogenic lead). This takes place via surface adsorption followed by rapid coupled dissolution-replacement driven incorporation throughout the grain. Results suggest that baryte may scavenge non-target elements during processing and contribute to an understanding of mobility, mineralogical location, and evolution in the deportment of radionuclides through the processing cycle.

Hematite (α-Fe2O3) has been successfully co-doped with uranium and lead using hydrated ferric oxide (HFO) as an intermediary, precipitated by ammonia from a ferric nitrate solution. A novel synthesis approach has been developed, involving a wet stage of doping colloidal HFO by absorption from nitrate solution containing U and Pb nitrates, followed by drying and heating to 700 °C to convert HFO to Fe2O3. The crystal phase present in the sample was confirmed as hematite by X-ray powder diffraction. Scanning electron microscopy was used to determine sample morphology and U/Pb isotope homogeneity was assessed using laser-ablation inductively-coupled-plasma mass spectrometry (LA-ICP-MS). Although reasonably homogeneous at the scale of a LA-ICP-MS ablation analysis spot, conspicuous domains are recognized that appear ‘bright’ or ‘dark’ on backscatter electron images. These domains display distinctly different element concentrations and U/Pb ratios on LA-ICP-MS isotope maps. Nevertheless, this synthetic U-Pb-doped hematite represents a potential reference material for use in microbeam U-Pb geochronology and the results show that the preparation methods and doping conditions are effective. The observed chemical and isotopic heterogeneity between bright and dark domains may, however, inhibit widespread use of the synthesized hematite as a reference material. U/Pb heterogeneity may be controlled by the heating and cooling regimes of the method. Assuming the ‘bright and dark domains’ can be analytically or mechanically separated through refinement of the preparation method, then a suitable reference material may be produced. Subject to validation via high-precision chemical analysis, this reference material can be used to date uranium-bearing hematite from various types of deposits. The high speed and precision of LA-ICP-MS analyses will allow measurement of geological ages in a very common mineral, providing new insights for mineral exploration worldwide.

The Middleback Ranges is a 60 km-long BIF-endowed iron ore belt located in the southeastern Gawler Craton and is the largest exploited iron resource in South Australia. The belt is hosted within an Archean- to Paleoproterozoic-aged granitic-gneissic basement terrane. Petrographic and geochronological constraints are given for a suite of granites associated with deposits throughout the Middleback Ranges and compared with other regional granites. Granites from the Middleback Ranges show complex mineralogical and geochemical features indicating multiple overprinting events. Sensitive high-resolution ion microprobe U-Pb zircon ages from all granites across the Middleback Ranges yield Archean ages, suggesting the existence and a more extensive distribution of Mesoarchean crust than previously recognized beneath the entire Middleback Ranges BIF sequence. Grey and pink granites from the central Middleback Ranges (Sultan prospect) produced the oldest 207Pb/206Pb weighted mean ages within the sample suite (3241 ± 6 and 3238 ± 9 Ma, respectively). Zircon in the latter granite also features overgrowths dated at ∼2.6 Ga and interpreted to be metamorphic. A second group of younger granites from the Iron Monarch deposit and a sample of Cooyerdoo Granite (northern Middleback Ranges) have a minimum crystallization age of 3165 ± 8 Ma and a 207Pb/206Pb weighted mean magmatic age of 3134 ± 18 Ma, respectively. The youngest granites analyzed here derive from the Iron Baron deposit in the central part of the belt, which display strong deformation and have a minimum crystallization age of 3089 ± 9 Ma, and from the Iron Magnet deposit in the southern part of the belt (207Pb/206Pb weighted mean age of 3023 ± 33 Ma). Petrographic and geochemical features observed within the sample suite indicate that post-Archean overprinting events led to alteration of the granitic basement and may infer that fluid-rock interaction and granite leaching were important for BIF upgrading processes and iron-oxide formation.

The Zhengguang gold deposit, a typical intermediate-sulfidation epithermal deposit, is located in the southeastern part of the Duobaoshan orefield, west of the Hegenshan-Heihe suture zone, in the eastern part of the Central Asian Orogenic Belt. The deposit comprises five ore zones with total Au reserves exceeding 35 tonnes, with potential additional resources at depth. All vein-type orebodies are hosted by Paleozoic volcanic rocks and comprise multiple vein sets 1–100 cm in thickness. Although gold generally occurs in native form, or as electrum in epithermal deposits like Zhengguang, both pyrite and sphalerite are known to accommodate modest concentrations of invisible gold. This study employs a combination of petrography and sulfide chemistry to determine the role of invisible gold in the Zhengguang ores and the mechanisms of gold incorporation into epithermal sulfides. Three sulfide stages are identified: an early quartz + pyrite (Py1a, Py1b) ± chalcopyrite (Ccp1) stage; a subsequent quartz + sphalerite (Sph2a, Sph2b) + pyrite (Py2a, Py2b, Py2c, Py2d) + chalcopyrite (Ccp2a, Ccp2b) ± galena ± calcite stage; and a late stage containing deformed quartz + pyrite (Py3a, Py3b) ± sphalerite. Petrography and sulfide chemistry allow three groups of pyrite (Au-poor, Au-rich, and a distinct Sb-rich group) to be distinguished, alongside three groups of chalcopyrite (Bi-rich, intermediate-Bi, and Bi-poor), and two groups of sphalerite (Au-poor, Au-rich). A potential porphyry system is indicated beneath the epithermal system by the appearance of Au-poor pyrite and Bi-poor chalcopyrite. After precipitation of early Au-poor sulfides, inflow of relatively low temperature epithermal fluids led to alteration and replacement of early porphyry-related sulfides, and to precipitation of Au-rich pyrite, Bi-rich and intermediate-Bi chalcopyrite, and sphalerite. Gold-rich pyrite contains up to 140 ppm Au, interpreted as both as lattice-scale substitution (Au1+) and as included particles of native gold (Au0). Epithermal chalcopyrite is an important silver carrier but, although Au is measurable, it is a not a good carrier for gold. A strong positive correlation between Au and Cu in pyrite from the first two stages indicate that gold and other metals were likely sourced from magma-derived hydrothermal fluids. The deposit was formed in the Early Paleozoic but some gold ores appear deformed and partially destroyed by a later metamorphic event during which a distinct Sb-rich pyrite crystallized. This study should catalyze exploration in the orefield as it provides further support for an as-yet undiscovered porphyry system close to the Zhengguang deposit.

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.

Florencite, [REEAl3(PO4)2(OH)6], is the most abundant REE-phosphate mineral in the giant Olympic Dam Cu-U-Au-Ag deposit, South Australia. Florencite typically occurs as fine-grained crystals and occasional aggregates in the matrix of the granite-dominant breccia that hosts the majority of the copper mineralization. Olympic Dam florencite, with the compositional range and extended formula (Ca0.01–0.24Sr0.03–0.40La0.14–0.49Ce0.20–0.47Pr0.00–0.03Nd0.00–0.05)Σ0.43–0.96Al2.89–3.33(P1.42–1.96S0.05–0.34As0.0–0.20)Σ1.77–2.21O4(OH)6], is LREE-enriched, typically La-dominant, while HREEs are minor. There is also compositional variability with respect to Sr, Ca, SO4, and AsO4 components. Chondrite-normalized fractionation trends are steeply downwards-sloping with a relatively low and flat HREE segment. Such a fractionation trend is markedly different from that seen for REE-fluorocarbonates, the dominant REE host at Olympic Dam, which contain relatively higher MREE and HREE components. Xenotime is relatively rare at Olympic Dam and is most commonly seen as overgrowths on zircon. Compositional data for xenotime show HREE concentrations in which Y > Yb > Er > Dy > Ho. Thorium, U, and Pb are minor components in both xenotime and florencite. Monazite is a minor phase and co-existing monazite and florencite are never observed. Texturally, florencite appears to belong to a later stage of LREE mineralization at Olympic Dam, following and less prominent than the main REE-fluorocarbonate stage. Olympic Dam florencite is more La-rich and Ca-poor than it is in most of the localities worldwide for which compositional data have been published. The REE mineralization trends of florencite are compared with published REE trends for other mineral groups from Olympic Dam. Uraninite, brannerite, coffinite, and apatite show patterns of progressive LREE depletion from generation to generation, suggesting enhanced solubility of LREE over geological time. All LREE minerals (fluorocarbonates and phosphates), on the other hand, display progressive LREE enrichment correlating with a paragenetic sequence from REE-fluorocarbonates with essential Ca, through bastnasite, to florencite. The late-stage florencite reported here is the most La-rich of all REE-bearing phases and is interpreted to record either the end of a continuous fluid evolution, or a later separate event at changed physicochemical conditions under which REE-aluminum phosphate minerals are stable.

This experimental study explored the potential of oral zinc sulfate to protect the gut mucosa from 5-fluorouracil (5-FU)-induced degenerative lesions in Wistar rats.Female Wistar rats were used and divided into 2 interventional groups (Z with 6 animals and F with 5 animals) and one control group (M with 5 rats). After 2 hours of fasting, group Z received via oral gavage 1.5 ml of solution, corresponding to 15 mg zinc sulfate for 9 consecutive days. Groups F and M received only the vehicles. On day 3, 400 mg/kg of 5-FU was administered intraperitoneally to groups Z and F. Tissue samples were collected from the duodenum, jejunum, colon and liver. Histological assessment for each gastrointestinal tract segment was determined semi-quantitatively by rating 11 histological features from normal (0) to severe (3). The independent groups were analyzed using the Kruskal-Wallis test and the Mann-Whitney U-test, with a Bonferroni correction for alpha (p ≤ 0.016).In group F the jejunum was the most affected area with a mean histological score of 27 (25-32). In the Z group, significantly lower histological scores were obtained compared with group F (duodenum Z vs. F: U = 0, p = 0.004; jejunum Z vs. F: U = 0, p = 0.006 and colon: Z vs. F: U = 0, p = 0.005). Graded liver necro-inflammatory lesions were significantly lower in group Z compared with group F (U = 0, p = 0.004), suggesting fewer bacterial intestinal translocation processes.Zinc sulfate has a beneficial role, decreasing the severity of gut mucosal injuries induced by 5-FU in Wistar rats.

Background Neopterin and RNA-ase are markers of inflammation with low disclosed role in diagnosis and prognosis of either STEMI or NSTEMI, although inflammation is well documented as a leader pathogenic mechanism in these pathologies. Aim Evaluation of serum admission levels of neopterin and ARN-ase in pts with STEMI and NSTEMI and their prediction value concerning the risk of MACE in 1 year of follow up period. Material and methods The admission serum concentration of neopterin and ARN-ase was determined by ELISA in 94 pts with STEMI and 92 pts with NSTEMI which was compared with normal markers appreciated in 32 healthy persons. Likewise, the rate of MACE in both groups was estimated during 1 year of post-infarction period. Diagnostic worth and MACE prediction power of markers have been established using respectively ROC curve and odds ratio. Results In patients with STEMI the serum level of neopterin was significantly increased compared with normal index by 3,5 times (11,6±3,4 vs 3,3±1,4 nM/L), but RNA-ase was significantly decreased by 43,4% (24,1±3,2 vs 42,6±5,2 nM/ml). In pts with NSTEMI neopterin level was lesser than STEMI, but significantly elevated by 39% (4,6±2,5 vs 3,3±1,4 nM/L) vs normal marker. RNA-ase level didn't significantly differ from normal level. However, adjusted to diabetes mellitus established in 19 pts, RNA-ase significantly diminished (36,4±3,9 vs 42,6±5,2 nM/ml), and its diagnostic value of NSTEMI according to ROC was 69,6% (RNA-ase level indicates inversely inflammation response, such as it breaks down extracellular RNA which has proinflammatory ability). Both markers in pts with NSTEMI and diabetes mellitus demonstrated a diagnostic value of 77,6%. In pts with STEMI highest tertile level of neopterin and lowest tertile level of ARN-ase had 2,8fold (adds ratio=2,8; CI=1,98–4,62; p Conclusions 1. In STEMI both neopterin and RNA-ase could be as diagnostic markers, due to their significant change. In NSTEMI neopterin significantly elevated, but RNA-ase didn't shift from normal. In diabetic pts with NSTEMI, however, their combination demonstrated in ROC estimation a diagnostic value of 77,6%. 2. Prediction value of markers combination regarding MACE risk in pts with NSTEMI is significant and close to each marker in partly prediction of MACE for pts with STEMI. Funding Acknowledgement Type of funding source: Public Institution(s). Main funding source(s): Research Institute of Cardiology, Moldova Republic of

Proximal and distal garnets from skarns at Jiaduobule, Tibet, are used to demonstrate how variation in the fluid composition and parameters such as salinity, pH, fO2, and $${\text{X}}_{{\rm CO}_{2}}$$ will impact on rare earth element (REE) distribution in garnets, and also to constrain skarn evolution across the orefield from proximal (Fe mineralization) to distal (Cu mineralization). These garnets display a diversity from proximal to distal skarn which is expressed in mineral assemblages, textures, major to trace element contents, and particularly, chondrite-normalized REE fractionation trends. The empirical variation among REE fractionation trends, determined from laser ablation inductively coupled-plasma mass spectrometry data, can be numerically modelled in terms of variable fluid compositions and physicochemical parameters, among which the key determining factors are salinity, pH, $${\text{X}}_{{{\text{CO}}_{{2}} }}$$ and Ca content buffered from the rock-fluid reaction with carbonate rocks. Modelling REE trends in skarn garnet is shown to be valuable for constraining conditions during garnet formation and a useful tool for monitoring the evolution of complex skarn deposits.

The Blackbush uranium prospect (~12,580 tonnes U at 85 ppm cut-off) is located on the Eyre Peninsula of South Australia. Blackbush was discovered in 2007 and is currently the single example of sediment-hosted uranium mineralisation investigated in any detail in the Gawler Craton. Uranium is hosted within Eocene sandstones of the Kanaka Beds and, subordinately, within a massive saprolite derived from the subjacent Hiltaba-aged (~1585 Ma) granites, affiliated with the Samphire Pluton. Uranium is mainly present as coffinite in different lithologies, mineralisation styles and mineral associations. In the sandstone and saprolite, coffinite occurs intergrown with framboidal Fe-sulphides and lignite, as well as coatings around, and filling fractures within, grains of quartz. Microprobe U&ndash, Pb dating of coffinite hosted in sedimentary units yielded a narrow age range, with a weighted average of 16.98 &plusmn, 0.16 Ma (343 individual analyses), strongly indicating a single coffinite-forming event at that time. Coffinite in subjacent saprolite generated a broader age range from 28 Ma to 20 Ma. Vein-hosted coffinite yielded similar ages (from 12 to 25 Ma), albeit with a greater range. Uraninite in the vein is distinctly older (42 to 38 Ma). The 17 &plusmn, 0.16 Ma age for sandstone-hosted mineralisation roughly coincides with tectonic movement as indicated by the presence of horst and graben structures in the Eocene sedimentary rocks hosting uranium mineralisation but not in stratigraphically younger sedimentary rocks. The new ages for hydrothermal minerals support a conceptual genetic model in which uranium was initially sourced from granite bedrock, then pre-concentrated into veins within that granite, and is subsequently dissolved and reprecipitated as coffinite in younger sediments as a result of low-temperature hydrothermal activity associated with tectonic events during the Tertiary. The ages obtained here for uranium minerals within the different lithologies in the Blackbush prospect support a conceptual genetic model in which tectonic movement along the reactivated Roopena Fault, which triggered the flow of U-rich fluids into the cover sequence. The timing of mineralisation provides information that can help optimise exploration programs for analogous uranium resources within shallow buried sediments across the region. The model presented here can be predicted to apply to sediment-hosted U-mineralisation in cratons elsewhere.