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Symplectites comprising clausthalite (PbSe) and host Cu-(Fe)-sulphides (chalcocite, bornite, and chalcopyrite) are instructive for constraining the genesis of Cu-Au-(U) ores if adequately addressed at the nanoscale. The present study is carried out on samples representative of all three Cu-(Fe)-sulphides displaying clausthalite inclusions that vary in size, from a few µm down to the nm-scale (<5 nm), as well as in morphology and inclusion density. A Transmission Electron Microscopy (TEM) study was undertaken on foils prepared by Focussed Ion Beam and included atom-scale High-Angle Annular Dark-Field Scanning TEM (HAADF-STEM) imaging. Emphasis is placed on phase relationships and their changes in speciation during cooling, as well as on boundaries between inclusions and host sulphide. Three species from the chalcocite group (Cu2-xS) are identified as 6a digenite superstructure, monoclinic chalcocite, and djurleite. Bornite is represented by superstructures, of which 2a and 4a are discussed here, placing constraints for ore formation at T > 265 °C. A minimum temperature of 165 °C is considered for clausthalite-bearing symplectites from the relationships with antiphase boundaries in 6a digenite. The results show that alongside rods, blebs, and needle-like grains of clausthalite within the chalcocite that likely formed via exsolution, a second, overprinting set of replacement textures, extending down to the nanoscale, occurs and affects the primary symplectites. In addition, other reactions between pre-existing Se, present in solid solution within the Cu-(Fe)-sulphides, and Pb, transported within a fluid phase, account for the formation of composite, commonly pore-attached PbSe and Bi-bearing nanoparticles within the chalcopyrite. The inferred reorganisation of PbSe nanoparticles into larger tetragonal superlattices represents a link between the solid solution and the symplectite formation and represents the first such example in natural materials. Epitaxial growth between clausthalite and monazite is further evidence for the interaction between pre-existing Cu ores and fluids carrying REE, P, and most likely Pb. In U-bearing ores, such Pb can form via decay of uranium within the ore, implying hydrothermal activity after the initial ore deposition. The U-Pb ages obtained for such ores therefore need to be carefully assessed as to whether they represent primary ore deposition or, more likely, an overprinting event. A latest phase of fluid infiltration is the recognised formation of Cu-selenide bellidoite (Cu2Se), as well as Fe oxides. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

Atomic-scale high angle annular dark field scanning transmission electron microscopy (HAADF STEM) imaging and electron diffractions are used to address the complexity of lattice-scale intergrowths of REE-fluorocarbonates from an occurrence adjacent to the Olympic Dam deposit, South Australia. The aims are to define the species present within the intergrowths and also assess the value of the HAADF STEM technique in resolving stacking sequences within mixed-layer compounds. Results provide insights into the definition of species and crystal-structural modularity. Lattice-scale intergrowths account for the compositional range between bastnäsite and parasite, as measured by electron probe microanalysis (at the µm-scale throughout the entire area of the intergrowths). These comprise rhythmic intervals of parisite and bastnäsite, or stacking sequences with gradational changes in the slab stacking between B, BBS and BS types (B--bastnäsite, S--synchysite). An additional occurrence of an unnamed B2S phase [CaCe3(CO3)4F3], up to 11 unit cells in width, is identified among sequences of parisite and bastnäsite within the studied lamellar intergrowths. Both B2S and associated parisite show hexagonal lattices, interpreted as 2H polytypes with c = 28 and 38 Å, respectively. 2H parisite is a new, short hexagonal polytype that can be added to the 14 previously reported polytypes (both hexagonal and rhombohedral) for this mineral. The correlation between satellite reflections and the number of layers along the stacking direction (c*) can be written empirically as: Nsat = [(m × 2) + (n × 4)] − 1 for all BmSn compounds with S ≠ 0. The present study shows intergrowths characterised by short-range stacking disorder and coherent changes in stacking along perpendicular directions. Knowing that the same compositional range can be expressed as long-period stacking compounds in the group, the present intergrowths are interpreted as being related to disequilibrium crystallisation followed by replacement. HAADF STEM imaging is found to be efficient for depiction of stacking sequences and their changes in mixed-layer compounds, particularly those in which heavy atoms, such as rare-earth elements, are essential components. [ABSTRACT FROM AUTHOR]

Olympic Dam is a world-class breccia-hosted iron-oxide copper-gold-uranium ore deposit located in the Gawler Craton, South Australia. It contains elevated concentrations of rare earth elements (REE) which occur as the REE minerals bastnäsite, synchysite, florencite, monazite, and xenotime. This is the first study to focus on the mineralogy and composition of the most abundant REE mineral at Olympic Dam, bastnäsite, and subordinate synchysite. The sample suite extends across the deposit and represents different sulfide mineralization styles (chalcopyrite-bornite and bornite-chalcocite) and breccias of various types, ranging from those dominated by clasts of granite, dykes, and hematite. The REE-fluorocarbonates (bastnäsite and synchysite) typically occur as fine-grained (<50 µm) disseminations in Cu-Fe-sulfides and gangue minerals, and also within breccia matrix. They are also locally concentrated within macroscopic REE-mineral-rich pockets at various locations across the deposit. Such coarse-grained samples formed the primary target of this study. Three general textural groups of bastnäsite are recognized: matrix (further divided into disseminated, fine-grained, and stubby types), irregular (sulfide-associated), and clast replacement. Textures are largely driven by the specific location and prevailing mineral assemblage, with morphology and grain size often controlled by the associated minerals (hematite, sulfides). Major element concentration data reveal limited compositional variation among the REE-fluorocarbonates; all are Ce-dominant. Subtle compositional differences among REE-fluorocarbonates define a spectrum from relatively La-enriched to (Ce + Nd)-enriched phases. Granite-derived hydrothermal fluids were the likely source of F in the REE-fluorocarbonates, as well as some of the CO2, which may also have been contributed by associated mafic-ultramafic magmatism. However, transport of REE by Cl-ligands is the most likely scenario. Stubby bastnäsite and synchysite may have formed earlier, coincident with hydrothermal alteration of granite releasing Ca from feldspars. Other categories of bastnäsite, notably those co-existing with sulfides, and reaching the top of the IOCG mineralization at Olympic Dam (chalcocite + bornite zone) are relatively younger. Such an interpretation is concordant with subtle changes in the REE patterns for the different categories. The common association of bastnäsite and fluorite throughout the deposit is typical of the hematite breccias and can be deposited from neutral, slightly acidic fluids (sericite stability) at T * 300 °C. [ABSTRACT FROM AUTHOR]

Minerals of the tetrahedrite isotypic series are widespread components of base metal ores, where they co-exist with common base metal sulphides (BMS) such as sphalerite, galena, and chalcopyrite. We used electron probe microanalysis and laser-ablation inductively-coupled plasma mass spectrometry to obtain quantitative multi-trace element data on tetrahedrite-tennantite in a suite of 37 samples from different deposits with the objective of understanding which trace elements can be incorporated, at what levels of concentration, and how the presence of tetrahedrite-tennantite influences patterns of trace element partitioning in base metal ores. Apart from Fe and Zn, Hg and Pb are the two most abundant divalent cations present in the analysed tetrahedrite-tennantite (up to 10.6 wt % Hg and 4 wt % Pb). Cadmium, Co and Mn are also often present at concentrations exceeding 1000 ppm. Apart from one particularly Te-rich tetrahedrite, most contained very little Te (around 1 ppm), irrespective of prevailing assemblage. Bismuth is a common minor component of tetrahedrite-tennantite (commonly > 1000 ppm). Tetrahedrite-tennantite typically hosts between 0.1 and 1000 ppm Se, while Sn concentrations are typically between 0.01 and 100 ppm. Concentrations of Ni, Ga, Mo, In, Au, and Tl are rarely, if ever, greater than 10 ppm in tetrahedrite-tennantite and measured W concentrations are consistently <1 ppm. Taking into account the trace element concentrations in co-crystallizing BMS, the results presented allow the partitioning trends between co-crystallized sphalerite, galena, chalcopyrite, and tetrahedrite-tennantite to be defined. In co-crystallizing BMS assemblages, tetrahedrite-tennantite will always be the primary host of Ag, Fe, Cu, Zn, As, and Sb, and will be the secondary host of Cd, Hg, and Bi. In contrast, tetrahedrite-tennantite is a poor host for the critical metals Ga, In, and Sn, all of which prefer to partition to co-crystallizing BMS. This study shows that tetrahedrite-tennantite is a significant carrier of a range of trace elements at concentrations measurable using contemporary instrumentation. This should be recognized when establishing protocols for trace element analysis of tetrahedrite-tennantite, and when assessing the main hosts of trace elements in any given assemblage, e.g., for geometallurgical purposes. [ABSTRACT FROM AUTHOR]

The textural relationships and geochemistry of feldspars from least-altered to sericite-hematite altered and mineralised ~ 1.595 Ga Roxby Downs Granite (RDG) at Olympic Dam, South Australia, were examined. The sample suite is representative of RDG both distal (> 5 km) and proximal (< 1 km) to the hydrothermal breccias of the Olympic Dam Breccia Complex (ODBC), which host Fe-oxide Cu-Au-(U) mineralisation at Olympic Dam. Microscopic observations and quantitative analyses indicate that a range of feldspar reactions have taken place within the RDG hosting the Olympic Dam deposit. An early phase of igneous plagioclase (~ An 27–34 ) is recognised, along with a more abundant, less-calcic plagioclase (~ An 12–20 ) both displaying rapakivi and anti-rapakivi textures with alkali feldspar. Alkali feldspars (~ Or 55 Ab 43 An 2 ) record post-magmatic evolution from cryptoperthite to patch perthite. Subsequent patch perthite is overprinted by highly porous, near end-member albite and K-feldspar, while plagioclase undergoes replacement by albite + sericite ± Ba-rich K-feldspar. In sericite-hematite altered and mineralised RDG along the margin of the ODBC, sericite replaces all plagioclase, whereas red-stained, Fe-rich K-feldspar persists. Sulphide-uranium-rare earth element mineralisation is observed in association with hydrothermal feldspars, and increases in abundance with proximity to the orebody. Petrographic observations and whole-rock geochemistry illustrate the transformation of plagioclase and alkali feldspar from igneous to hydrothermal processes, and indicate that hydrothermal albite and K-feldspar formed within the RDG without the need for an external source of alkalis. Feldspar geothermometry indicates a minimum crystallisation temperature of 765 °C at 2.2 kbar for alkali feldspar (pressure estimate obtained using plagioclase-amphibole geobarometry) followed by a range of lower temperature transformations. Late-stage magma mixing/contamination is postulated from supportive temperature and pressure estimates along with feldspar and mafic mineral relationships. [ABSTRACT FROM AUTHOR]

This paper comprises a review of the rapidly expanding application of nanoscale mineral characterization methodology to the study of ore deposits. Utilising bismuth sulphosalt minerals from a reaction front in a skarn assemblage as an example, we illustrate how a complex problem in ore petrology, can be approached at scales down to that of single atoms. We demonstrate the interpretive opportunities that can be realised by doing this for other minerals within their petrogenetic contexts. From an area defined as Au-rich within a sulphosalt-sulphide assemblage, and using samples prepared on a Focused Ion Beam-Scanning Electron Microscopy (SEM) platform, we identify mineral species and trace the evolution of their intergrowths down to the atomic scale. Our approach progresses from a petrographic and trace element study of a larger polished block, to high-resolution Transmission Electron Microscopy (TEM) and High Angle Annular Dark Field (HAADF) Scanning-TEM (STEM) studies. Lattice-scale heterogeneity imaged in HAADF STEM mode is expressed by changes in composition of unit cell slabs followed by nanoparticle formation and their growth into "veins". We report a progressive transition from sulphosalt species which host lattice-bound Au (neyite, lillianite homologues; Pb-Bi-sulphosalts), to those that cannot accept Au (aikinite). This transition acts as a crystal structural barrier for Au. Fine particles of native gold track this progression over the scale of several hundred microns, leading to Au enrichment at the reaction front defined by an increase in the Cu gradient (several wt %), and abrupt changes in sulphosalt speciation from Pb-Bi-sulphosalts to aikinite. Atom-scale resolution imaging in HAADF STEM mode allows for the direct visualisation of the three component slabs in the neyite crystal structure, one of the largest and complex sulphosalts of boxwork-type. We show for the first time the presence of aikinite nanoparticles a few nanometres in size, occurring on distinct (111)PbS slabs in the neyite. This directly explains the non-stoichiometry of this phase, particularly with respect to Cu. Such non-stoichiometry is discussed elsewhere as defining distinct mineral species. The interplay between modular crystal structures and trace element behaviour, as discussed here for Au and Cu, has applications for other mineral systems. These include the incorporation and release of critical metals in sulphides, heavy elements (U, Pb, W) in iron oxides, the distribution of rare earth elements (REE), Y, and chalcophile elements (Mo, As) in calcic garnets, and the identification of nanometre-sized particles containing daughter products of radioactive decay in ores, concentrates, and tailings. [ABSTRACT FROM AUTHOR]

Laser ablation inductively-coupled plasma mass spectrometry (LA-ICP-MS) has rapidly established itself as the method of choice for generation of multi-element datasets for specific minerals, with broad applications in Earth science. Variation in absolute concentrations of different trace elements within common, widely distributed phases, such as pyrite, iron-oxides (magnetite and hematite), and key accessory minerals, such as apatite and titanite, can be particularly valuable for understanding processes of ore formation, and when trace element distributions vary systematically within a mineral system, for a vector approach in mineral exploration. LA-ICP-MS trace element data can assist in element deportment and geometallurgical studies, providing proof of which minerals host key elements of economic relevance, or elements that are deleterious to various metallurgical processes. This contribution reviews recent advances in LA-ICP-MS methodology, reference standards, the application of the method to new mineral matrices, outstanding analytical uncertainties that impact on the quality and usefulness of trace element data, and future applications of the technique. We illustrate how data interpretation is highly dependent on an adequate understanding of prevailing mineral textures, geological history, and in some cases, crystal structure. [ABSTRACT FROM AUTHOR]

Constraints on accurate quantitative trace element and sulfur (S) isotope analysis of sulfide minerals, especially pyrite, by laser-ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) remain imperfectly understood at the present time. Mapping of S isotope distributions within a complex sample containing several minerals requires an evaluation of the matrix effects and accuracy. Here, we apply LA-Q(quadrupole)-ICP-MS and LA-MC(multiple collector)-ICP-MS methods to analyze trace elements and S isotopes in sulfides. Spot analysis of S isotopes was conducted to evaluate the influence of matrix effects. The matrix effects from siderite and magnetite are deemed to be negligible in mapping analysis at the precision of this study. Both Fe and S were used as internal standard elements to normalize trace element concentrations in pyrite. Fe proved to be the better choice because the normalized counts per second ratio of trace elements with Fe is much more stable than if using S. A case study of a sulfide sample from the Chengmenshan Cu deposit, Jiangxi Province, South China, demonstrates the potential of combined S isotope and trace element mapping by LA-(MC)-ICP-MS. The results suggest that this deposit underwent multi-stage ore formation. Elements, including Au and Ag, were hosted in early-stage pyrite but were re-concentrated into multi-component sulfide assemblages during a late-stage hydrothermal event, which also led to crosscutting veins containing pyrite largely devoid of trace elements, except Se. Combining in situ S isotope and trace element analysis on the same sample represents a powerful tool for understanding ore-forming processes. [ABSTRACT FROM AUTHOR]

The > 10,000 million tonne Olympic Dam Cu–Au–U–Ag deposit, (eastern Gawler Craton, South Australia) is one of the largest orebodies in the World. The deposit is hosted within the Olympic Dam Breccia Complex, placed at the centre of, and resulting from multiple brecciation and Fe-metasomatism of the Roxby Downs Granite (RDG). The latter is part of a larger batholith emplaced at ~ 1.6 Ga. Apatite petrography and chemistry were studied in non-mineralised RDG and coeval granitoids and dolerites, as well as in mineralised RDG from deep (> 2 km) and distal (2.7 km to NE) locations. In both latter cases, although the mineralisation corresponds to the same, early chalcopyrite–pyrite–magnetite ± hematite stage identified in the outer and deeper zones of the deposit itself, the character of granite alteration differs: sericite–chlorite alteration with all feldspar replaced in the deep location; and red-stained K-feldspar on top of prevailing albitization in the distal location. Close-to end-member fluorapatite is a key accessory mineral in all igneous rocks and a common product of early hydrothermal alteration within mineralised granite. Variations in habit, morphology and textures correlate with chemical trends expressed as evolving Cl/F ratios, and concentrations of REE + Y (hereafter REY), Sr, Mn, S, Si and Na. Magmatic apatite is unzoned in the dolerite but features core to REY-enriched rim zonation in the granitoids. Increases in Cl- and Sr-contents correlate with rock basicity. Calculation of Cl in the vapour phase relative to melt at the apatite saturation temperature for zoned apatite in the RDG shows higher values for grains with inclusion-rich cores associated with mafic enclaves, concordant with assimilation of exotic material during magma crystallisation. Hydrothermal alteration of magmatic apatite is most varied in the dolerite where interaction with fluids is expressed as subtle changes in Cl- versus F- and REY-enrichment, and most importantly, S-enrichment in grains adjacent to crosscutting, carbonate–sulphide-bearing veins. Highly acidic fluids, which not only corroded apatite but also quartz, led to recycling of REY via subsequent crystallisation of discrete REY-bearing species, notably monazite. Hydrothermal apatite often occurs as interstitial aggregates and displays a wider range of textures indicating variability in local growth conditions and/or sustained interaction with evolving hydrothermal fluids. Apatite from the deep mineralisation is richer in Cl whereas increases in ΣREY and S correlate with higher Si in both deep and distal cases. The co-correlation between Na and S in apatite from distal mineralisation ties apatite crystallisation to replacement of albite by sericite + chlorite. The textural and chemical variation of apatite relative to magmatic to hydrothermal transition suggests that the mineral represents a petrogenetic tool to gain insights into mineralising processes at Olympic Dam. Apatite evolution clearly played a key contributing role in the elevated REY-concentrations seen at Olympic Dam. The marked differences in apatite chemistry between mineralised and non-mineralised lithologies show promise for potential application as a tool in mineral exploration, in which apatite chemistry represents a means for outlining spatial position within an alteration envelope, or identifying if a particular alteration system is barren or fertile with respect to Cu–Au mineralisation. [ABSTRACT FROM AUTHOR]

Trace element concentrations in garnet and associated minerals from the mid-Miocene Zhibula Cu skarn, Gangdese Belt, Tibet reflect a diversity of local environments, evolving fluid parameters and partitioning with coexisting minerals. Exoskarn occurs as massive but narrow intervals within a Lower Jurassic volcano-sedimentary sequence containing limestone, the main skarn protolith. Endoskarn is present at the contact with mid-Miocene granodiorite dikes. Prograde skarn associations are garnet-dominant but also include diopside-dominant pyroxene in variable amounts. Garnet compositions in exoskarn change from andradite (And)- to grossular (Gr)-dominant from the massive intervals to bands/lenses within marble/tuff, but not in endoskarn. In both cases however, associations at the protolith contact include anorthite and wollastonite, both indicative of skarnoid or distal (relative to fluid source) skarn formation. Exoskarns also contain vesuvianite. Retrograde clinozoisite, actinolite and chlorite replace pre-existing skarn minerals. Garnet displays brecciation and replacement by Al-richer garnet. Depending on partitioning among coexisting minerals, chondrite-normalised REY (REE + Y) fractionation trends for garnet depict endo- to exoskarn diversity, the dominance of And- vs. Gr-rich garnet (in turn related to proximal-to-distal relationship to fluid source), as well as prograde-to-retrograde evolution in the same sample. A strong variation in Eu-anomaly, from positive to negative, in And-dominant garnet can be correlated with variation in salinity of ore-forming fluids, concordant with published fluid inclusion data. Trends depicted by And- and Gr-dominant garnets are consistent with published data from skarns elsewhere, in which the dominant substitution mechanism for REY is YAG-type. Zhibula garnets are enriched in a range of trace elements less commonly reported, including W, Sn, and As, but also Mo (as high as 730 ppm), an element seldom analysed for in silicates. Molybdenum, W, and Sn display excellent co-correlation and shared zonation patterns on LA–ICP–MS maps of garnet, indicating substitution in the crystal lattice. As well as assisting in interpreting skarn evolution in time and space, and providing constraints on ore genesis, the trace element data for garnet explain the range of colours observed. The discovery of garnets carrying significant concentrations of W, Sn and Mo is a valuable finding that deserves evaluation in post-collisional skarns elsewhere, and is potentially of critical significance in prospecting. Together with a conspicuous trace ore mineral signature, garnet compositions at Zhibula support a genetic connection and sharing of ore-forming fluids between the skarn and the Qulong porphyry Cu-Mo deposit, 2 km to the north. Within the Gangdese belt, or in analogous settings elsewhere, the presence of deep-seated porphyry mineralization beneath exposed skarns could be tested for by studying garnet chemistry. As more data become available, such trace element signatures could be viable tools for distinguishing barren from mineralized skarn systems. [ABSTRACT FROM AUTHOR]

U–Pb dating of the common iron-oxide hematite (α-Fe2O3), using laser-ablation inductively-coupled-plasma mass-spectrometry (LA-ICP-MS), provides unparalleled insight into the timing and processes of mineral deposit formation. Until now, the full potential of this method has been negatively impacted by the lack of suitable matrix-matched standards. To achieve matrix-matching, we report an approach in which a U–Pb solution and ablated material from 99.99% synthetic hematite are simultaneously mixed in a nebulizer chamber and introduced to the ICP-MS. The standard solution contains fixed U- and Pb-isotope ratios, calibrated independently, and aspiration of the isotopically homogeneous solution negates the need for a matrix-matched, isotopically homogenous natural iron-oxide standard. An additional advantage of using the solution is that the individual U–Pb concentrations and isotope ratios can be adjusted to approximate that in the unknown, making the method efficient for dating hematite containing low (~10 ppm) to high (>1 wt %) U concentrations. The above-mentioned advantage to this solution method results in reliable datasets, with arguably-better accuracy in measuring U–Pb ratios than using GJ-1 Zircon as the primary standard, which cannot be employed for such low U concentrations. Statistical overlaps between 207Pb/206Pb weighted average ages (using GJ-1 Zircon) and U–Pb upper intercept ages (using the U–Pb mixed solution method) of two samples from iron-oxide copper-gold (IOCG) deposits in South Australia demonstrate that, although fractionation associated with a non-matrix matched standard does occur when using GJ-1 Zircon as the primary standard, it does not impact the 207Pb/206Pb or upper intercept age. Thus, GJ-1 Zircon can be considered reliable for dating hematite using LA-ICP-MS. Downhole fractionation of 206Pb/238U is observed to occur in spot analyses of hematite. The use of rasters in future studies will hopefully minimize this problem, allowing for matrix-matched data. Using the mixed-solution method in this study, we have validated a published hematite Pb–Pb age for Olympic Dam, and provide a new age (1604 ± 11 Ma) for a second deposit in the same province. These ages are further evidence that the IOCG mineralizing event is tied to large igneous province (LIP) magmatism in the region at ~1.6 Ga. [ABSTRACT FROM AUTHOR]

The distribution and substitution mechanism of Ge in the Ge-rich sphalerite from the Tres Marias Zn deposit, Mexico, was studied using a combination of techniques at µm- to atomic scales. Trace element mapping by Laser Ablation Inductively Coupled Mass Spectrometry shows that Ge is enriched in the same bands as Fe, and that Ge-rich sphalerite also contains measurable levels of several other minor elements, including As, Pb and Tl. Micron- to nanoscale heterogeneity in the sample, both textural and compositional, is revealed by investigation using Focused Ion Beam-Scanning Electron Microscopy (FIB-SEM) combined with Synchrotron X-ray Fluorescence mapping and High-Resolution Transmission Electron Microscopy imaging of FIB-prepared samples. Results show that Ge is preferentially incorporated within Fe-rich sphalerite with textural complexity finer than that of the microbeam used for the X-ray Absorption Near Edge Structure (XANES) measurements. Such heterogeneity, expressed as intergrowths between 3C sphalerite and 2H wurtzite on zones, could be the result of either a primary growth process, or alternatively, polystage crystallization, in which early Fe-Ge-rich sphalerite is partially replaced by Fe-Ge-poor wurtzite. FIB-SEM imaging shows evidence for replacement supporting the latter. Transformation of sphalerite into wurtzite is promoted by (111)* twinning or lattice-scale defects, leading to a heterogeneous ZnS sample, in which the dominant component, sphalerite, can host up to ~20% wurtzite. Ge K-edge XANES spectra for this sphalerite are identical to those of the germanite and argyrodite standards and the synthetic chalcogenide glasses GeS2 and GeSe2, indicating the Ge formally exists in the tetravalent form in this sphalerite. Fe K-edge XANES spectra for the same sample indicate that Fe is present mainly as Fe2+, and Cu K-edge XANES spectra are characteristic for Cu+. Since there is no evidence for coupled substitution involving a monovalent element, we propose that Ge4+ substitutes for (Zn2+, Fe2+) with vacancies in the structure to compensate for charge balance. This study shows the utility of synchrotron radiation combined with electron beam micro-analysis in investigating low-level concentrations of minor metals in common sulfides. [ABSTRACT FROM AUTHOR]

Minor and trace elements can substitute into the crystal lattice of galena at various concentrations. In situ LA-ICP-MS analysis and trace element mapping of a range of galena specimens from different deposit types are used to obtain minor/trace element data, aimed at achieving insight into factors that control minor/trace element partitioning. The previously recognized coupled substitution Ag++(Bi,Sb)3+ ↔ 2Pb2+ is confirmed. However, the poorer correlation between Ag and (Bi+Sb) when the latter elements are present at high concentrations (~>2000 ppm), suggests that site vacancies may come into play: [2(Bi,Sb)3++ ↔ 3Pb2+]. Galena is the primary host of Tl in all mapped mineral assemblages. Along with Cu, Tl is likely incorporated into galena via the coupled substitution: (Ag,Cu,Tl)++(Bi,Sb)3+ ↔ 2Pb2+. Tin can reach significant concentrations in galena (>500 ppm). Cd and minor Hg can be incorporated into galena; the simple isovalent substitution (Cd,Hg)2+ ↔ Pb2+ is inferred. This paper shows for the first time, oscillatory and sector compositional zoning of minor/trace elements (Ag, Sb, Bi, Se, Te, Tl) in galena from two epithermal ores. Zoning is attributed to slow crystal growth into open spaces within the vein at relatively low temperatures. The present data show that galena can host a broader range of elements than previously recognized. For many measured elements, the data sets generated display predictable partitioning patterns between galena and coexisting minerals, which may be dependent on temperature or other factors. Trace element concentrations in galena and their grain-scale distributions may also have potential in the identification of spatial and/or temporal trends within individual metallogenic belts, and as markers of ore formation processes in deposits that have undergone superimposed metamorphism and deformation. Galena trace element geochemistry may also display potential to be used as a trace/minor element vector approach in mineral exploration, notably for recognition of proximal-to-distal trends within a given ore system. [ABSTRACT FROM AUTHOR]

Laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) spot analysis and element mapping coupled with high-resolution focused ion beam-scanning electron microscopy (FIB-SEM) imaging has been performed on Au-hosting sulfides from a Proterozoic orogenic gold deposit, Tanami gold province, north-central Australia. Gold distribution patterns in the arsenopyrite-pyrite assemblage, which probably crystallized toward the end of the Au-forming event, suggest a process of initial scavenging of Au into arsenopyrite and subsequent remobilization of that An following brittle fracture. Gold expelled from the sulfide lattice during the remobilization event is reconcentrated around the margins of the same arsenopyrite grains and within swarms of crosscutting microfractures. The distribution of Pb, Bi, and Ag closely mimic Au, indicating that these elements were also reconcentrated. Preservation of oscillatory zonation patterns for Co, Ni, Sb, Se, and Te in arsenopyrite imply, however, that no significant degree of sulfide reciystallization took place. Residual concentrations of invisible gold (in grain centers) are <5 ppm in arsenopyrite and <1 ppm in coexisting pyrite. The presence of submicron-sized pores is suggestive of a fluid-driven process rather than solid state diffusion. Micron-scale (2-10 µm) remobilized gold is accompanied by fine particles (200 nm-2 µm) and nanoparticles (<200 nm) of gold. The extensive variation of Au concentrations within single arsenopyrite grains underlines the significance of textures when using trace element data to understand how gold ores evolved. [ABSTRACT FROM AUTHOR]

Pyrite, the most abundant sulfide on Earth and a common component of gold deposits, can be a significant host for refractory gold. This is the first documentation of pore-attached, composite Au-telluride nanoparticles in "arsenic-free" pyrite. Trace elements mapping in pyrite from an intrusion-hosted Au deposit with orogenic overprint (Dongping, China) shows trails of tellurides overlapping Co-Ni-zonation. Intragranular microfracturing, anomalous anisotropy, and high porosity are all features consistent with devolatilization attributable to the orogenic event. The pyrite-hosted nanoparticles are likely the "frozen," solid expression of Te-rich, Au-Ag-Pb-bearing vapors discharged at this stage. Nanoparticle formation, as presented here, provides the "smallest-scale" tool to fingerprint Au-trapping during crustal metamorphism [ABSTRACT FROM AUTHOR]

In situ spatially resolved X-ray absorption near edge structure (m-XANES) spectra are obtained for natural Cu-In-bearing sphalerite. Copper K-edge spectral data show that, in Cu-In-bearing sphalerite, in which an excellent correlation between the Cu and In contents is noted, Cu is present in the Cu+ state. This offers indirect proof for the coupled substitution 2 Zn2+ ↔ Cu+ + In3+, which allows indium to enter the sphalerite structure. The study clearly demonstrates the utility of synchrotron radiation to accurately determine oxidation state in small volumes of mineral in which the concentration of the element of interest is low or very low. The study also demonstrates that good quality m-XANES spectra can be collected on TEM foils prepared in situ at a chosen position on the surface of a polished sample using the focused ion beam-scanning electron microscope method. [ABSTRACT FROM AUTHOR]

Chalcocite, bornite, and chalcopyrite are the main copper minerals in the world-class Olympic Dam Cu-U-Au-Ag deposit, South Australia. Olympic Dam is characterized by systematic, inwards and upwards zonation of Cu-Fe-sulfide assemblages, encompassing chalcopyrite-pyrite, bornite-chalcopyrite, bornite-chalcocite and chalcocite-only zones. Trace element analysis of Cu-(Fe)-sulfides (~ 3500 spot analyses) by laser ablation inductively coupled plasma mass spectrometry on samples from across the deposit identifies the role of spatial position, protolith, and the presence/absence of co-existing sulfides (sphalerite, tetrahedrite-tennantite and carrollite) in control of trace element endowment. Cu-(Fe)-sulfides host concentrations of precious metals (Ag, Au), potential value-add elements (Se, Te, Bi, As, Sb, In) and deleterious elements (Pb, Hg). Where bornite-chalcocite co-exist, Ag is partitioned into chalcocite and Bi into bornite; in the absence of either bornite or chalcocite, chalcopyrite is a significant host for both elements. Chalcocite from the chalcocite-only zone is depleted in Bi-Te-Ag-Au compared to the bornite-chalcocite zone, demonstrating the role of bornite as an initial scavenger of these elements. A distinct inherited Cr-Ni-Zn signature is identified in chalcopyrite hosted by banded iron formation derived lithologies and proximal to crosscutting dykes. Despite some variation, Cu-(Fe)-sulfides generally contain more Bi and lesser Se towards deeper levels. The concentrations of these elements in paired bornite-chalcocite assemblages show promise as ore vectors, whereas Ag/Te in brown bornite and Se/Ag in chalcopyrite are prospective lateral vectors. Results carry implications for understanding deposit evolution, provide insights towards developing reconnaissance exploration vectors, and offer guidance on trace element deportments likely to impact ore quality and geometallurgical performance. [ABSTRACT FROM AUTHOR]

The Irish Orefield is characterised by the presence of both Zn-Pb- and Cu-Ni-As-rich deposits, prospects, and orebodies in similar structural and stratigraphic positions. However, the genetic relationships between these mineralisation types are still debated. In this article, we present new mineralogical, paragenetic, and mineral-chemical observations from the Cu-Ni-As-rich ores at the classic Lisheen deposit, County Tipperary. These observations indicate the intimate association and cogenetic nature of these ores with the more abundant Zn-Pb-rich mineralisation. Specifically, both mineralisation types appear to have formed at the same time, under similar physicochemical conditions, and from the same ore fluids. In addition, both types of mineralisation contain elevated Ge contents. The cogenetic nature of the two mineralisation types, the relative absence of Cu-Ni-As-rich ores from most of the larger Irish-type Zn-Pb deposits compared to expectations derived from probable ore fluid compositions, and finally, the known geological characteristics of larger Cu-Ni-As-rich ore bodies, like Gortdrum, indicate that significant Cu-Ni-As-rich mineralisation could be present at lower stratigraphic levels across the Irish Orefield. Areas with extensive known Zn-Pb mineralisation are expected to be particularly prospective for such ores, which may occur at stratigraphic levels as deep as the Old Red Sandstone. This may have additional implications beyond Ireland, and could point to the potential for undiscovered Cu-rich ores in low-temperature carbonate-hosted Zn-Pb districts elsewhere. [ABSTRACT FROM AUTHOR]

Bi8Te3 is a member of the tetradymite homologous series, previously shown to be compositionally and structurally distinct from hedleyite, Bi7Te3, yet inadequately characterized structurally. The phase is identified in a sample from the Hedley district, British Columbia, Canada. Compositions are documented by electron probe microanalysis and structures are directly imaged using high-angle annular dark field (HAADF) scanning transmission electron microscopy (STEM). Results confirm that Bi8Te3 has an 11-atom layer structure, in which three Bi-Bi pairs are placed adjacent to the five-atom sequence (Te-Bi-Te-Bi-Te). Bi8Te3 has trigonal symmetry (space group R 3 ¯ m) with unit cell dimensions of a = ~4.4 Å and c = ~63 Å calculated from measurements on representative electron diffraction patterns. The model is assessed by STEM simulations and EDS mapping, all displaying good agreement with the HAADF STEM imaging. Lattice-scale intergrowths are documented in phases replacing Bi8Te3, accounting for the rarity of this phase in nature. These results support prior predictions of crystal structures in the tetradymite homologous series from theoretical modeling and indicate that other phases are likely to exist for future discovery. Tetradymite homologues are mixed-layer compounds derived as one-dimensional superstructures of a basic rhombohedral sub-cell. Each member of the series has a discrete stoichiometric composition and unique crystal structure. [ABSTRACT FROM AUTHOR]

• U-bearing magnetite is characterised from the outer shell of the Olympic Dam deposit. • LA-ICP-MS U-Pb dating of magnetite generates reproducible ~1760 Ma 207Pb206Pb dates. • First recognition of incorporated protoliths predating deposit formation at ~1590 Ma. • U-rich iron formations may provide additional sources of U and Fe to IOCG systems. Spatial associations between banded iron formation and iron-oxide Cu-Au (IOCG) style mineralization are well documented in the Gawler Craton (South Australia), but the possible genetic relationships between these two distinct types of mineralization are hitherto unclear. A texturally conspicuous generation of coarse-grained silician magnetite, intergrown with carbonates and quartz, is observed in drillholes intersecting the 'outer shell' of the Olympic Dam IOCG-type deposit. This magnetite is characterised by high U-content (~50 ppm), siliceous chemistry, and unusual zonal textures with respect to Si-Fe-nanoprecipitates. Direct dating of this magnetite by laser ablation inductively coupled plasma mass spectrometry yields reproducible 207Pb/206Pb dates (1761 ± 16 Ma) that are significantly older than the granite hosting the deposit (1593 Ma), or the mineralized breccias constituting the Cu-U-Au-Ag resource (~1592–1589 Ma). The older, Fe-rich crustal material can be correlated with the ~1.76–1.74 Ga (meta)sedimentary Wallaroo Group, host to Fe-rich horizons across the Gawler Craton, including locations ~15 km NW of Olympic Dam. A generation of granitic rocks, which intruded bedrock at ~1.75 Ga are present ~30 km NE of Olympic Dam, and likely exsolved hydrothermal fluids that enriched pre-existing magnetite-bearing protoliths in both U and REE. Such material was physically, and likely chemically, incorporated into the 'outer shell' at Olympic Dam some ~150 Ma later, during granite uplift along faults. The coincidence between Fe-rich horizons/BIF and ~1750 Ma granitoids may have provided IOCG systems with an additional source of both Fe and U that predates the ~1.59 Ga craton-scale metallogenic event. The uranium concentrations in some South Australian IOCG systems represent major global anomalies in the element. A combination of the fortuitous geological circumstances outlined here, may help explain the highly anomalous accumulation of uranium found at Olympic Dam. [ABSTRACT FROM AUTHOR]

Finding direct evidence for hydrous fluids on early Mars is of interest for understanding the origin of water on rocky planets, surface processes, and conditions essential for habitability, but it is challenging to obtain from martian meteorites. Micro-to nanoscale microscopy of a unique impact-shocked zircon from the regolith breccia meteorite NWA7034 reveals textural and chemical indicators of hydrothermal conditions on Mars during crystallization 4.45 billion years ago. Element distribution maps show sharp alternating zoning defined by marked enrichments of non-formula elements, such as Fe, Al, and Na, and ubiquitous nanoscale magnetite inclusions. The zoning and inclusions are similar to those reported in terrestrial zircon crystallizing in the presence of aqueous fluid and are here interpreted as primary features recording zircon growth from exsolved hydrous fluids at ~4.45 billion years. The unique record of crustal processes preserved in this grain survived early impact bombardment and provides previously unidentified petrological evidence for a wet pre-Noachian martian crust. [ABSTRACT FROM AUTHOR]

The incorporation of impurity elements into minerals impacts their physical properties (e.g., reflectance, hardness, and electrical conductivity), but the quantitative relationships between these features and compositional variation remain inadequately constrained. Prior work has shown that gamma-enhancement of reflected light images represents a simple yet powerful tool to assess the compositional heterogeneity of single pyrite crystals, as it can enhance subtle differences in reflectance between distinct domains with different minor element concentrations. This study extends the gamma correction method to several other common Fe-bearing minerals, magnetite, garnet, wolframite, and tetrahedrite-tennantite, which all have far lower reflectance than pyrite. Gamma-enhanced optical images reveal clear variations in reflectance that are either systematic with increased minor element concentration, as the change in gray value on backscatter electron (BSE) images (in the case of magnetite, garnet, and tetrahedrite-tennantite) or contrasting (as in pyrite), yielding a convincing linkage between reflectance variation and compositional heterogeneity. Reflectance variation is an expression of the distribution of the average effective number of free electrons on the mineral surface that can re-emit light when excited by visible light. Gamma-enhanced images can reveal compositional heterogeneity in minerals such as wolframite where small atomic mass differences between substituting elements (Mn and Fe, in the case of wolframite) are virtually impossible to observe as a variation of gray values on BSE images. Results also demonstrate that Fe-rich domains in these minerals can be expected to have higher reflectance than Fe-poor domains whenever Fe is a major constituent. The greater reflectance is attributed to Fe ions having a greater effective number of free electrons than many other elements (e.g., Co, Ni, Si, Ca, Al, Mg, Mn, and As). This research highlights the utility of gamma correction as an inexpensive tool for routine evaluation of compositional heterogeneity in common Fe-bearing minerals, potentially obviating the necessity of a microbeam platform to correlate textures and composition. [ABSTRACT FROM AUTHOR]

• BIF-associated mafic magmatism constrained by petrography and U-Pb geochronology. • ~2.5 Ga mafic sills interbedded with BIFs are metamorphosed to amphibolites. • First confirmation of Gairdner LIP dolerites in Middleback Ranges. • Second burial and ore upgrading constrained from U-Pb hematite age at ~680 Ma. Banded iron formation (BIF)-derived iron ore deposits of the Middleback Ranges, Eyre Peninsula, South Australia, are hosted within Archean to Paleoproterozoic basement in the southeastern Gawler Craton. Mafic sills and dikes are associated with the orebodies throughout the belt and although described previously, have never been studied in detail. Two main types of mafic rocks, amphibolites and dolerites, are distinguishable from field occurrence and mineralogy. Amphibolites interbedded with BIFs from the southern Iron Magnet deposit are characterized by extensive overprinting. These amphibolites contain metamorphic assemblages of coexisting Mg-Fe- and Ca-amphiboles, garnet, corundum, biotite and relict titaniferous magnetite displaying ilmenite exsolution. Amphibolite petrography and geochemistry in the southern part of the belt indicate formation in a complex BIF depositional environment, with possible detrital input of titaniferous magnetite from igneous rocks. In contrast, NW-trending dolerite dikes occur throughout the belt and contain assemblages consisting of igneous magnesiohornblende and plagioclase. SHRIMP U–Pb zircon ages for amphibolites and dolerites yield two age groups. Amphibolite from Iron Magnet yields a 207Pb/206Pb weighted mean age of 2542 ± 15 Ma. The most robust 206Pb/238U weighted mean age of 782 ± 23 Ma for dolerites comes from the Iron Queen deposit in the central part of the Middleback Ranges. LA-ICP-MS U–Pb geochronology of U-bearing hematite from the Iron Knight South deposit yields ages of ~680 Ma. Taken together, these results suggest mafic magmatism contemporaneous with Archean BIF deposition followed by a high-grade metamorphic event (~2.47–2.41 Ga Sleafordian Orogeny). Dikes from Cape Donington, the southernmost point on the Eyre Peninsula are, instead, associated with the 1.73–1.69 Ga Kimban Orogeny, as evidenced by zircon from a pyroxene-rich dolerite, which yields a 206Pb/238U weighted mean age of 1711 ± 14 Ma. The dolerite ages from the Iron Queen deposit provide the first evidence for the presence of the ~800 Ma craton-scale Gairdner Large Igneous Province in the Middleback Ranges. The young U–Pb hematite age from Iron Knight South and post-emplacement alteration of dikes of Gairdner age from the central part of the Middleback Ranges belt provide additional support for multiple events leading to upgrading of iron ores. [ABSTRACT FROM AUTHOR]

Titanite textures and chemistry have been investigated from the Roxby Downs Granite, host to the Olympic Dam Cu–U–Au–Ag deposit, South Australia. Three textural subtypes of titanite are documented: primary magmatic (cores and rims); deuteric; and hydrothermal (low T recrystallisation). Magmatic cores are defined by enrichment in LREE (~ 3 wt%), Nb (up to 1 wt%) and Zr relative to rims, which typically contain < 1 wt% LREE and Nb, as well as greater concentrations of Al, Ca, Fe and F. Deuteric titanite occurs as overgrowths on pre-existing titanite and other magmatic accessory minerals (magnetite and ilmenite), and is depleted in HFSE compared to magmatic rims, showing geochemical trends consistent with substitution of Ca2+ + Ti4+ ↔ REE3+ + (Al, Fe)3+. Hydrothermal titanite forms as a low-temperature hydrothermal overprint on primary titanite as well as an alteration product of chloritised phlogopite. Applying Zr-in-titanite geothermometry, three temperature ranges are obtained for titanite crystallisation: magmatic cores ~ 765 to 780 °C; rims ~ 705 to 740 °C; and deuteric ~ 680 to 690 °C. Titanite breakdown is a ubiquitous feature of the Roxby Downs Granite, and occurs through interaction with CO2- and F-rich fluids, forming pseudomorphs characterised by the presence of REE-fluorocarbonates, which are subsequently overprinted by REE-phosphates with increased proximity to the Olympic Dam Breccia Complex. This change is related to interaction with fluids containing appreciable PO42− liberated from local dissolution of fluorapatite. Such observations are consistent with and linked to later/retrograde stages in the formation of the Olympic Dam deposit. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

Zirconium is an element of considerable petrogenetic significance but is rarely found in hematite at concentrations higher than a few parts-per-million (ppm). Coarse-grained hematite ore from the metamorphosed Peculiar Knob iron deposit, South Australia, contains anomalous concentrations of Zr and has been investigated using microanalytical techniques that can bridge the micron- to nanoscales to understand the distribution of Zr in the ore. Hematite displays textures attributable to annealing under conditions of high-grade metamorphism, deformation twins (r~85° to hematite elongation), relict magnetite and fields of sub-micron-wide inclusions of baddeleyite as conjugate needles with orientation at ~110°/70°. Skeletal and granoblastic zircon, containing only a few ppm U, are both present interstitial to hematite. Using laser-ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) spot analysis and mapping, the concentration of Zr in hematite is determined to be ~260 ppm on average (up to 680 ppm). The Zr content is, however, directly attributable to nm-scale inclusions of baddeleyite pervasively distributed throughout the hematite rather than Zr in solid solution. Distinction between nm-scale inclusions and lattice-bound trace element substitutions cannot be made from LA-ICP-MS data alone and requires nanoscale characterization. Scandium-rich (up to 0.18 wt. % Sc2O3) cores in zircon are documented by microprobe analysis and mapping. Using high-angle annular dark field scanning transmission electron microscopy imaging (HAADF-STEM) and energy-dispersive spectrometry STEM mapping of foils prepared in-situ by focused ion beam methods, we identify [ 0 1 ¯ 1 ]baddeleyite epitaxially intergrown with [ 2 2 ¯.1 ]hematite. Lattice vectors at 84–86° underpinning the epitaxial intergrowth orientation correspond to directions of r-twins but not to the orientation of the needles, which display a ~15° misfit. This is attributable to directions of trellis exsolutions in a precursor titanomagnetite. U–Pb dating of zircon gives a 206Pb/238U weighted mean age of 1741 ± 49 Ma (sensitive high-resolution ion microprobe U–Pb method). Based on the findings presented here, detrital titanomagnetite from erosion of mafic rocks is considered the most likely source for Zr, Ti, Cr and Sc. Whether such detrital horizons accumulated in a basin with chemical precipitation of Fe-minerals (banded iron formation) is debatable, but such Fe-rich sediments clearly included detrital horizons. Martitization during the diagenesis-supergene enrichment cycle was followed by high-grade metamorphism during the ~1.73–1.69 Ga Kimban Orogeny during which martite recrystallized as granoblastic hematite. Later interaction with hydrothermal fluids associated with ~1.6 Ga Hiltaba-granitoids led to W, Sn and Sb enrichment in the hematite. By reconstructing the evolution of the massive orebody at Peculiar Knob, we show how application of complimentary advanced microanalytical techniques, in-situ and on the same material but at different scales, provides critical constraints on ore-forming processes. [ABSTRACT FROM AUTHOR]

The distributions of 210Pb and 210Po, short half-life products of 238U decay, in geological and related anthropogenic materials are reviewed, with emphasis on their geochemical behaviours and likely mineral hosts. Concentrations of natural 210Pb and 210Po in igneous and related hydrothermal environments are governed by release from crustal reservoirs. 210Po may undergo volatilisation, inducing disequilibrium in magmatic systems. In sedimentary environments (marine, lacustrine, deltaic and fluvial), as in soils, concentrations of 210Pb and 210Po are commonly derived from a combination of natural and anthropogenic sources. Enhanced concentrations of both radionuclides are reported in media from a variety of industrial operations, including uranium mill tailings, waste from phosphoric acid production, oil and gas exploitation and energy production from coals, as well as in residues from the mining and smelting of uranium-bearing copper ores. Although the mineral hosts of the two radionuclides in most solid media are readily defined as those containing parent 238U and 226Ra, their distributions in some hydrothermal U-bearing ores and the products of processing those ores are much less well constrained. Much of the present understanding of these radionuclides is based on indirect data rather than direct observation and potential hosts are likely to be diverse, with deportments depending on the local geochemical environment. Some predictions can nevertheless be made based on the geochemical properties of 210Pb and 210Po and those of the intermediate products of 238U decay, including isotopes of Ra and Rn. Alongside all U-bearing minerals, the potential hosts of 210Pb and 210Po may include Pb-bearing chalcogenides such as galena, as well as a range of sulphates, carbonates, and Fe-oxides. 210Pb and 210Po are also likely to occur as nanoparticles adsorbed onto the surface of other minerals, such as clays, Fe-(hydr)oxides and possibly also carbonates. In rocks, unsupported 210Pb- and/or 210Po-bearing nanoparticles may also be present within micro-fractures in minerals and at the interfaces of mineral grains. Despite forming under very limited and special conditions, the local-scale isotopic disequilibrium they infer is highly relevant for understanding their distributions in mineralized rocks and processing products. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

• Compositional data for copper anodes from Olympic Dam (Australia) are given. • Trace element impurities are homogeneously distributed at the scale of the anode. • LA-ICP-MS analysis allows quantification of trace elements in solid solution. • Impurities also occur as micron-scale impurity inclusions containing multiple phases. • Nanoscale particles containing impurity elements are also present in copper. Anode copper is the intermediate product between copper smelting and electrorefining. Anodes are typically 98.5 to 99.8 % pure and require electrorefining to high-purity copper cathode that can be sold to customers. Impurity elements, including Ag, Au, As, Sb, Bi, Se, Te, Sn, Pb, Co, and Ni (alongside minor Fe, Al, and Si), are either dissolved within anode copper, or contained within micron-scale inclusions. To better understand the distribution of these impurities, a study of anode copper was undertaken on representative samples from the Olympic Dam anode plant, South Australia. Bulk assay for 61 elements of 269 sub-samples collected on a grid across a single anode, including the 'ears', shows homogeneity irrespective of location. The five most abundant impurity elements are As (mean 1279 ± 41 ppm), Se (218 ± 11 ppm), Sb (211 ± 8 ppm), Bi (202 ± 9 ppm), and Ni (195 ± 6 ppm). The assay data demonstrate that reliable, representative compositional data on the anode can be obtained from sampling and assay of only a limited part of the whole, including the 'ears'. Trace element analysis of copper metal by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) allows quantification of dissolved minor components. Some metals, notably Ni, occur almost completely dissolved in copper. Other elements occur only partially in dissolved form, but the proportions measured in copper metal relative to bulk assay vary significantly from only ∼ 9 % for Pb, 13 % for Bi and Te, 25 % for Se, 29 % for Sn, 34 % for Sb, 55 % for As, and 60–70 % for Au, Ag, and Co. These results are consistent with the observation of a diverse suite of 1–10 µm-sized, rounded impurity inclusions containing Pb, Bi, As, Sb, Te, Se etc. that are associated with cuprite, Cu 2 O, and largely follow copper grain boundaries. The inclusions, each containing one or more crystalline (e.g., Cu-selenides, some Cu-Bi-arsenates, Sn-oxides and cuprite) and/or glassy phases (e.g., Cu-Pb-As-Sb-Bi-oxides), represents a trapped melt droplet, leading to the observed broad range of compositions. [ABSTRACT FROM AUTHOR]

Hematite (α-Fe 2 O 3) 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. • New methodology for ID-TIMS, SHRIMP and LA-ICP-MS hematite U-Pb geochronology, isotope mapping and in-situ grain extraction • The U-Pb systematics of compositionally and morphologically distinct samples from Olympic Dam are evaluated • Hematite is a remarkably robust mineral for constraining ore forming processes [ABSTRACT FROM AUTHOR]

• The chemistry of anode slimes from the Olympic Dam electrorefinery is described. • Decopperisation results in replacement and redistribution of Sb, Se and Te. • Gold occurs dissolved in Cu-Ag- and Ag-selenides and microgranular Ag 3 Au(Se,Te) 2. • Nanoscale imaging confirms α-BiAsO 4 , corresponding to the mineral rooseveltite. • EBSD methods enable rapid assessment of crystallinity in individual particles. Together with silver (Ag) and gold (Au), which are almost always recovered, the impurity elements, arsenic (As), antimony (Sb), bismuth (Bi), tin (Sn), lead (Pb), selenium (Se) and tellurium (Te) are major components of anode slimes, a by-product of the electrorefining of impure copper. The Olympic Dam electrorefinery, South Australia, generates raw slimes (∼30 % Cu, 5–10 % Ag, 0.5–1 % Au, 3–4 % Bi, ∼2–3 % Sb, and 5–6 % As), which subsequently undergo decopperisation and then pH-neutralisation. Decopperisation involves treatment with steam and acid at 90 °C, giving a slime that contains ∼ 1 % Cu, 8–17 % Ag, ∼2% Au, ∼7% Bi, ∼4–5 % Sb, and ∼ 3 % As. pH-neutralisation is achieved by addition of NaOH and is the final step prior to cyanidation and precious metal recovery. Bulk chemical compositions, gross morphology and particle size distributions are complemented by high-magnification backscatter imaging and energy-dispersive X-ray analysis of individual particles in raw, decopperised, and pH-neutralised anode slimes. In a first micron-to-nanoscale approach, we use electron backscatter diffraction mapping to assess the crystallinity of individual component phases and a scanning transmission electron microscopy study on micron-sized slices extracted in-situ to confirm the crystal structure of a conspicuous BiAsO 4 phase as rooseveltite. The results establish an in-depth understanding of element deportments in slimes and their evolution during sequential stages of treatment. Characterisation studies for Te, Se, Sb, Bi, and As are essential prerequisites for any design of metallurgical circuits for by-product recovery from anode slimes and/or electrolyte. This study aims to demonstrate that complementary cutting-edge microanalytical techniques widely used in mineralogy provide a level of detail essential when considering refinery slimes as a new source of critical commodities. [ABSTRACT FROM AUTHOR]

Graphical abstract Highlights • First definition of geochemical IOCG mineralisation signature in the Olympic Dam. • The IOCG signature is formed by associations of Cu-U 3 O 8 -Se-S and Au-W-Mo-As-Sb. • Au-W-Mo-Sb-As forms a ∼1800 m deep corridor in the south-eastern lobe of the deposit. • The PCA allows delineation of ore body within a disseminated ore deposit. Abstract 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-U 3 O 8 -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. [ABSTRACT FROM AUTHOR]

Uni- and multivariate statistical analyses of trace element laser-ablation inductively coupled plasma mass spectrometry data for Fe-oxides from banded iron formation (BIF) and BIF-hosted ores in 13 deposits/prospects of the Middleback Ranges, South Australia are presented. The obtained trace element signatures were considered within a petrographic-textural framework of iron-oxide evolution from magnetite through clean martite and porous martite to platy hematite, to evaluate changes in trace element concentrations with respect to the ore enrichment processes. Statistically valid distinctions among different hematite textures were indicated for most trace elements by linear mixed-effects models. Furthermore, the hematite data showed significant intra-class correlations between spot-analyses within individual polished blocks and correlations between polished blocks within individual deposits. The data are thus aggregated within their hierarchical levels. Two linear discriminant function analyses were performed to determine the combinations of trace elements that can distinguish hematite by textures and by location within the Middleback Ranges. Tin, a significant discriminator element in both models, reflects the regional influence of granite-affiliated hydrothermal fluids on the clean martite. This granitic signature, therefore, postdates formation of magnetite BIFs and potentially represents a supergene ore enrichment stage. The combination of Ni, Co, Ti and Nb was discovered to be uniquely attributed to discrimination of the Northern and Southern Middleback Ranges, indicating very specific local settings unrelated to hematite textures. Both local and regional settings impacting on the trace element signatures of Fe-oxides throughout iron ore formation are recognised, suggesting distinct ore enrichment conditions within various segments of the belt. [ABSTRACT FROM AUTHOR]

The new mineral grațianite, MnBi2S4, is described from the Băița Bihor skarn deposit, Bihor County. Romania. Grațianite occurs as thin lamellae, intimately intergrown with cosalite and bismuthinite, or as flower-shaped blebs within chalcopyrite, where it is associated with cosalite and tetradymite. Grațianite displays weak to modest bireflectance in air and oil, respectively, and strong anisotropy. The mean empirical composition based on 20 electron probe microanalyses is: (Mn0.541Fe0.319Pb0.070Cu0.040 Cd0.009Ag0.001)Σ0.980(Bi1.975Sb0.018)Σ1.993(S4.008Se0.012Te0.007)Σ4.027, corresponding to the ideal formula MnBi2S4. Grațianite crystallizes in the monoclinic system (space group Cllm). Single-crystal X-ray studies of material extracted by the focused ion beam-scanning electron microscopy (FIB-SEM) technique, and carried out on the MX2 macromolecular beamline of the Australian Synchrotron determined the following cell dimensions: α = 12.6774(25) Å, b = 3.9140(8) Å, c = 14.7581(30) Å, β = 115.31(3)°, V= 662.0(2) ų, and Z = 4. The six strongest X-ray reflections and their relative intensities are: 3.448 Å (100), 2.731 Å (77), 2.855 Å (64), 3.637 Å (55), 3.644 Å (54), and 3.062 Å (51). Grațianite is the monoclinic analog of berthierite (FeSb2S4), garavellite [Fe(Bi,Sb)2S4] and clerite [Mn(SbAs)2S4] (Nickel-Strunz class 02.HA.20). It is isostructural with synthetic sulfides and selenides in the MnBi2S4-MnSb2S4 and MnBi2Se4-MnSb2Se4 series, and with grumiplucite (HgBi2S4) and ku-driavite, [(Cd,Pb)Bi2S4], ³P members of the pavonite homologous series. The mineral is named for Grațian Cioflica (1927-2002), formerly Professor in Mineralogy and Ore Deposits at the University of Bucharest, Romania. The Băița Bihor skarn, like others within the same belt, is geochemically complex. The availability of Cu, Zn, and Pb, but also Ag, Bi, Mo, and B, as well as a wide range of minor elements, has created an environment allowing for crystallization of an unusually diverse range of discrete minerals. Grațianite is part of the peculiar associations of Bi--Pb-sulfosalts and Bi-chalcogenides that are genetically related to Au-enrichment. This study demonstrates the versatility of FIB-SEM techniques for in situ extraction of small volumes of well-characterized material, coupled with single-crystal X-ray analysis using synchrotron radiation, for the characterization of new minerals. [ABSTRACT FROM AUTHOR]

This study reports a detailed evaluation of how key parameters of operation influence the measurement of sulfur isotopes using laser ablation multiple collector inductively coupled plasma mass spectrometry (LA-MC-ICP-MS). Sulfur isotopes are observed to display a fractionation up to 2‰ δ 34 S during analysis of pyrite with different laser parameters using a 193 nm ArF excimer laser. In order to understand why the laser parameters affect S isotope fractionation when measuring S isotopes in pyrite, Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM) techniques were used to characterize debris formed during the ablation of pyrite, i.e., morphology and speciation of phases. The results show that pyrite decomposes to two phases: ball-like troilite (FeS) and a sulfur-rich floc-like agglomeration surrounding the troilite. The measured δ 34 S values vary due to the different proportions of troilite balls and the floc-like material generated under different laser parameters. The proportion of troilite and S was evaluated with a LA-(Quadrupole)-ICP-MS through direct comparison of the counts per second (CPS) ratio of 56 Fe to 32 S. In contrast to pyrite, natural pyrrhotite shows no decomposition process and the particle size of the debris from pyrrhotite is nearly 10 times larger than that of pyrite (~ 5 μm for pyrrhotite compared to < 1 μm for pyrite). Therefore, a biased analysis of pyrite may happen using laser ablation although this problem can be minimized using high raster velocity. Last but not least, we provide a case study of S isotope mapping using high raster velocity, which extends the application of the in-situ S isotope analysis technique. The results here carry implications for the choice of settings needed to obtain accurate LA-MC-ICP-MS S-isotope maps of pyrite. [ABSTRACT FROM AUTHOR]

There is an abundance of published trace element data for sphalerite, galena and chalcopyrite in natural systems, yet for a co-crystallized assemblage comprising these base metal sulphides, there is no detailed understanding of the preferred host of many trace elements. Laser-ablation inductively-coupled plasma mass spectrometry trace element maps and spot analyses were generated on 17 assemblages containing co-crystallized sphalerite and/or galena and/or chalcopyrite from 9 different ore deposits. These deposits are representative of different ore types, geologic environments and physiochemical conditions of ore formation, as well as superimposed syn-metamorphic remobilisation and recrystallization. The primary factors that control the preferred base metal sulphide host of Mn, Fe, Co, Cu, Zn, Ga, As, Se, Ag, Cd, In, Sb, Te, Tl and Bi are element oxidation state, ionic radius of the substituting element, element availability and the maximum trace element budget that a given sulphide mineral can accommodate. Temperature, pressure, redox conditions at time of crystallization and metal source, do not generally appear to influence the preferred base metal sulphide host of all the trace elements. Exceptions are Ga, In and Sn recrystallized at high metamorphic grades, when the preferred host of Ga and Sn usually becomes chalcopyrite. In more typical lower temperature ores, the preferred host of Ga is sphalerite. Indium concentrations also increase in chalcopyrite during recrystallization. At lower temperatures the partitioning behaviour of Sn remains poorly constrained and shows little predictable pattern among the data here. The results obtained may be used as a tool to assess co-crystallization. If trace element distributions in a given base metal sulphide assemblage match those reported here, and assuming those distributions have not been significantly altered post (re-) crystallization, then it may be suggestive of a co-crystallized assemblage. Such information provides a foundation for novel attempts to develop trace element-in-sulphide geothermometers. [ABSTRACT FROM AUTHOR]