Feldspar mineralogy and rare-earth element (re)mobilization in iron-oxide copper gold systems from South Australia: a nanoscale study

Nanoscale characterization (TEM on FIB-SEM-prepared foils) was undertaken on feldspars undergoing transformation from early post-magmatic (deuteric) to hydrothermal stages in granites hosting the Olympic Dam Cu-U-Au-Ag deposit, and from the Cu-Au skarn at Hillside within the same iron-oxide copper-gold (IOCG) province, South Australia. These include complex perthitic textures, anomalously Ba-, Fe-, or REE-rich compositions, andREE-flourocarbonate + molybdenite assemblages which pseudomorph pre-existing feldspars. Epitaxial orientations between cryptoperthite (magmatic), patch perthite (dueteric) and replacive albite (hydrothermal) within vein perthite support interface-mediated reactions between pre-existing alkali-feldspars and pervading fluid, irrespective of micro-scale crystal morphology. Such observations are consistent with a coupled dissolution-reprecipitation reaction mechanism, which assists in grain-scale element remobilization via the generation of transient interconnected microporosity. Micro-scale aggregates of hydrothermal hyalophane (Ba-rich K-feldspar), crystallizing within previously albitized areas of andesine, reveal a complex assemblage of calc-silicate, As-bearing fluorapatite and Fe oxides along reaction boundaries in the enclosing albite-sericite assemblage typical of deuteric alteration. Such inclusions are good REE repositories and their presence supports REE remobilization at the grain-scale during early hydrothermal alteration. Iron-metasomatism is recognized by nanoscale maghemite inclusions within ‘red-stained’ orthoclase, as well as by hematite in REE-fluorocarbonates, which reflect broader-scale zonation patterns typical for IOCG systems. Potassium-feldspar from the contact between alkali-granite and skarn at Hillside is characterized by 100–1000 ppm REE, attributable to pervasive nanoscale inclusions of calc-silicates, concentrated along microfractures, or pore-attached. Feldspar replacement by REE-fluorcarbonates at Olympic Dam and nanoscale calc-silicate inclusions in feldspar at Hillside are both strong evidence for the role of feldspars in concentrating REE during intense metasomatism. Differences in mineralogical expression are due to the availability of associated elements. Lattice-scale intergrowths of assemblages indicative of Fe-metasomatism, REE-enrichment and sulfide deposition at Olympic Dam are evidence for a spatial and temporal relationship between these processes

Tin-bearing magnetite with nanoscale Mg-Si defects: Evidence for the early stages of mineralization in a skarn system

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 <111*> directions in magnetite

Focused Ion Beam and Advanced Electron Microscopy for Minerals: Insights and Outlook from Bismuth Sulphosalts

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

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

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

Short-Range Stacking Disorder in Mixed-Layer Compounds: A HAADF STEM Study of Bastnäsite-Parisite Intergrowths

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

Copper-Bearing Magnetite and Delafossite in Copper Smelter Slags

The cooling paths and kinetics in the system Cu-Fe-O are investigated by the empirical micro- and nanoscale analysis of slags from the flash furnace smelter at Olympic Dam, South Australia. We aim to constrain the exsolution mechanism of delafossite (Cu1+Fe3+O2) from a spinel solid solution (magnetite, Fe3O4) and understand why cuprospinel (CuFe2O4) is never observed, even though, as a species isostructural with magnetite, it might be expected to form. Flash furnace slags produced in the direct-to-blister copper smelter at Olympic Dam contain four Cu-bearing phases: Cu-bearing magnetite, delafossite, metallic copper, and cuprite. Delafossite coexists with magnetite as rims and lamellar exsolutions, as well as bladed aggregates, associated with cuprite within Si-rich glass. The empirical compositions of magnetite and rim delafossite are (Fe2+6.89Cu2+0.86Co0.13Mg0.15Si0.02)8.05 (Fe3+15.52Al0.41Ti0.01Cr0.01)15.95O32, and (Cu1+0.993Co0.002Mg0.002)0.997(Fe3+0.957Al0.027Ti0.005Si0.004)0.993O2, respectively. The measured Cu content of magnetite represents a combination of a solid solution (~6 mol.% cuprospinel endmember) and exsolved delafossite lamellae. Atomic-resolution high-angle annular dark field scanning transmission electron microscope (HAADF STEM) imaging shows epitaxial relationships between delafossite lamellae and host magnetite. Defects promoting the formation of copper nanoparticles towards the lamellae margins suggest rapid kinetics. Dynamic crystallization under locally induced stress in a supercooled system (glass) is recognized from misorientation lamellae in delafossite formed outside magnetite grains. The observations are concordant with crystallization during the cooling of molten slag from 1300 °C to <1080 °C. Melt separation through an immiscibility gap below the solvus in the system Cu-Fe-O is invoked to form the two distinct delafossite associations: (i) melt-1 from which magnetite + delafossite form; and (ii) melt-2 from which delafossite + cuprite form. Such a path also corroborates the published data explaining the lack of cuprospinel as a discrete phase in the slag. Delafossite rims form on magnetite at a peritectic temperature of ~1150 °C via a reaction between the magnetite and copper incorporated in the oxide/Si-rich melt. The confirmation of such a reaction is supported by the observed misfit orientation (~10°) between the rim delafossite and magnetite. HAADF STEM imaging represents a hitherto underutilized tool for understanding pyrometallurgical processes, and offers a direct visualization of phase relationships at the smallest scale that can complement both experimental approaches and theoretical studies based on thermodynamic modelling

Feldspar mineralogy and rare-earth element (re)mobilization in iron-oxide copper gold systems from South Australia: a nanoscale study

Nanoscale characterization (TEM on FIB-SEM-prepared foils) was undertaken on feldspars undergoing transformation from early post-magmatic (deuteric) to hydrothermal stages in granites hosting the Olympic Dam Cu-U-Au-Ag deposit, and from the Cu-Au skarn at Hillside within the same iron-oxide copper-gold (IOCG) province, South Australia. These include complex perthitic textures, anomalously Ba-, Fe-, or REE-rich compositions, andREE-flourocarbonate + molybdenite assemblages which pseudomorph pre-existing feldspars. Epitaxial orientations between cryptoperthite (magmatic), patch perthite (dueteric) and replacive albite (hydrothermal) within vein perthite support interface-mediated reactions between pre-existing alkali-feldspars and pervading fluid, irrespective of micro-scale crystal morphology. Such observations are consistent with a coupled dissolution-reprecipitation reaction mechanism, which assists in grain-scale element remobilization via the generation of transient interconnected microporosity. Micro-scale aggregates of hydrothermal hyalophane (Ba-rich K-feldspar), crystallizing within previously albitized areas of andesine, reveal a complex assemblage of calc-silicate, As-bearing fluorapatite and Fe oxides along reaction boundaries in the enclosing albite-sericite assemblage typical of deuteric alteration. Such inclusions are good REE repositories and their presence supports REE remobilization at the grain-scale during early hydrothermal alteration. Iron-metasomatism is recognized by nanoscale maghemite inclusions within ‘red-stained’ orthoclase, as well as by hematite in REE-fluorocarbonates, which reflect broader-scale zonation patterns typical for IOCG systems. Potassium-feldspar from the contact between alkali-granite and skarn at Hillside is characterized by 100–1000 ppm REE, attributable to pervasive nanoscale inclusions of calc-silicates, concentrated along microfractures, or pore-attached. Feldspar replacement by REE-fluorcarbonates at Olympic Dam and nanoscale calc-silicate inclusions in feldspar at Hillside are both strong evidence for the role of feldspars in concentrating REE during intense metasomatism. Differences in mineralogical expression are due to the availability of associated elements. Lattice-scale intergrowths of assemblages indicative of Fe-metasomatism, REE-enrichment and sulfide deposition at Olympic Dam are evidence for a spatial and temporal relationship between these processes

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

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

210pb and 210po in geological and related anthropogenic materials: Implications for their mineralogical distribution in base metal ores

The distributions of Pb-210 and Po-210, short half-life products of U-238 decay, in geological and related anthropogenic materials are reviewed, with emphasis on their geochemical behaviours and likely mineral hosts. Concentrations of natural Pb-210 and Po-210 in igneous and related hydrothermal environments are governed by release from crustal reservoirs. Po-210 may undergo volatilisation, inducing disequilibrium in magmatic systems. In sedimentary environments (marine, lacustrine, deltaic and fluvial), as in soils, concentrations of Pb-210 and Po-210 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 U-238 and Ra-226, 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 Pb-210 and Po-210 and those of the intermediate products of U-238 decay, including isotopes of Ra and Rn. Alongside all U-bearing minerals, the potential hosts of Pb-210 and Po-210 may include Pb-bearing chalcogenides such as galena, as well as a range of sulphates, carbonates, and Fe-oxides. Pb-210 and Po-210 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 Pb-210- and/or Po-210-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