Search

Sulfosalt assemblages in a specimen from the Boliden Au–Cu–(As) deposit in northern Sweden, comprise micrometre to nanometre scale intergrowths of Se-rich izoklakeite and tintinaite with average formulae and calculated homologue number (N) given as: (Cu1.88Fe0.18)2.06(Pb22.92Ag1.47Cd0.01Zn0.01)24.41(Sb13.12Bi8.69)21.8(S50.19Se6.43Te0.12)56.73, N = 3.83, and (Cu1.31Fe0.74)2.05(Pb10.58Ag0.18Cd0.05Zn0.02)10.83(Sb10.2Bi5.23)15.43(S32.22Se2.46)34.7, N = 2.05, respectively. Tintinaite coexists with (Bi, Se)-rich jamesonite. High-angle annular dark field scanning transmission electron microscopy (HAADF STEM) imaging reveals chessboard structures comprising PbS and SnS modules with the number of atoms in the octahedral (M) sites counted as: n 1 = 18 and n 2 = 8 for tintinaite and n 1 = 30 and n 2 = 16 for izoklakeite. The homologue number can be calculated using the formula: N = (n 1/6)–1 and N = n 2/4 for PbS and SnS modules giving N Tti = 2 and N Iz = 4. A new N = 3 homologue, defined by n = 12 and n = 24 SnS and PbS modules, respectively, is identified as single or double units within areas with intergrowths between kobellite and izoklakeite. HAADF STEM imaging also reveals features attributable to lone electron pair micelles within the Sb-rich kobellite homologues. Atomic-resolution EDS STEM chemical mapping of Pb–Bi–Sb-sulfosalts shows a correlation with crystal structural modularity. The maps also highlight sites in the SnS modules of tintinaite in which Sb > Bi. Coherent nanoscale intergrowths between tintinaite and izoklakeite define jigsaw patterns evolving from chessboard structures and are considered to have formed during co-crystallisation of the two phases. Displacement textures and crosscutting veinlets (a few nm in width) are interpreted as evidence for superimposed syn-metamorphic deformation and are associated with the redistribution of Bi and Se. Imaging and mapping using HAADF STEM techniques is well suited to characterisation of Pb–Sb–Bi-sulfosalt phases, offering largely untapped potential to unravel the evolution of chessboard structures with applications across mineralogy but also extending into allied fields. [ABSTRACT FROM AUTHOR]

Non-classical pyriboles (NCPs) have tetrahedral silicate chains (Ibeam) of multiplicity higher than single (pyroxene) or double (amphibole) Ibeams and are known from amphiboles in altered mafic-ultramafic complexes. NCPs, their polysomatic sequences, and inherent chain-width disorder are petrogenetic tools for interpreting igneous and metamorphic processes. Magnetite, a refractory mineral that can trap and preserve NCPs is a major constituent of iron oxide-copper-gold (IOCG) deposits. We undertook a nanoscale study to show that NCPs and amphiboles are hosted within magnetite cores from the Jatobá Ni-bearing IOCG deposit, Carajás Mineral Province, Brazil. Monoclinic amphiboles and NCPs form polysomatic intergrowths or occur as sparse inclusions along {111}magnetite. There are two chemical populations of amphiboles: Mg-Fe- and Ca-(Al)-amphiboles, the latter including Ce-bearing Mg-hornblende and (ferro)tschermakite. The occurrence contains one of the widest ranges of chain silicates ever recorded, from simple intergrowths of single to triple Ibeam zippers, including pyroxene slabs, to longer NCP polysomes up to 15-Ibeam chains. Clinojimthompsonite (Cjim) is observed for the first time within magnetite. Although no discrete polysomes could be defined, the NCP-amphibole intergrowths have compositions between Mg-Fe amphiboles and Cjim based on Ibeam averages of 2.5–2.7. Relationships between increase in the number of C and A cations from amphibole (2-Ibeam) to n chain silicates (nIbeam) are formulated as nIbeam = T(2 + n) = C(5 + 3n) = A(1 + n), n = integer. Empirical models of crystal structures, validated by STEM simulation, are shown for 4- and 5-Ibeam chain silicates. Co-crystallization of double- and triple-chain silicate structures with rhythmic intergrowths as larger blocks along b is often accompanied by rhythmic Ca-Fe zonation along a, supporting primary NCP crystallization via self-patterning during amphibole growth within magnetite in a close-to-equilibrium system. Chain-width disorder is documented from defects including planar faults, derailments, jogs, and swells. Violations of zipper termination rules indicate primary growth rather than replacement. Amphibole-NCPs inclusions support a multi-stage evolution for Jatobá magnetite. They formed during the first cycle of magnetite overprinting within a mafic/ultramafic lithology that records syn-shearing events. Subsequent formation of calcic-amphiboles, including Ce-bearing species, indicate IOCG-related fluids at the onset of mineralization. (Ferro) tschermakite formed at ~7.5 kbar during high-pressure shearing is preserved during main ore deposition. The multi-stage amphibole-NCPs generations in magnetite revealed by our nanoscale study emphasize the interpretive value of magnetite for overprinting events in terranes with protracted geological histories. Analogous NCPs are likely to be abundant in magnetite from magmatic-hydrothermal deposits hosted by greenstone belts and altered mafic/ultramafic complexes. Likewise, discovery of Ce-rich hornblende provides new avenues to understand the early, alkali-calcic alteration stages of IOCG systems and models for REE incorporation into, and subsequent release from chain silicates. [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]

Clogauite, ideally PbBi4Te4S3 is the new n = 1 member of the aleksite series, Pb n Bi4Te4S n+2, where n is the homologue number. Clogauite is named from the type locality, the Clogau gold mine, Dolgellau Gold belt, Gwynedd, North Wales, United Kingdom. The mineral and name have been approved by the Commission on New Minerals, Nomenclature and Classification of the International Mineralogical Association (IMA2023–062). The aleksite series is an accretional homologous series in which each member is derived from the same 5-atom tetradymite archetype. Clogauite crystallises in the trigonal crystal system (space group: P $\bar{3}$ m 1, #164). Three distinct polytypes of clogauite are recognised, corresponding to identical chemistry but different layer sequences, expressed as (57), (5559) and (557.559), respectively, in reference to the number of atoms in individual layer sequences. These are clogauite-12 H , a = 4.277(4) Å, c = 23.46(14) Å, V = 371.598 Å3 and Z = 1; clogauite-24 H , a = 4.278(4) Å, c = 46.88(31) Å, V = 743.053 Å3 and Z = 2; and clogauite-36 H , a = 4.278(4) Å, c = 70.36(32) Å, V = 1115.283 Å3 and Z = 3. Clogauite is opaque, with a pale grey colour in reflected light. Reflectance is higher than tetradymite or galena. Bireflectance and anisotropy are strong. Structural data were determined from measurement of atomic-scale HAADF STEM imaging showing the internal arrangement of component atoms and characteristic selected area electron diffraction patterns for each polytype. The structures were then further constrained from ab initio total energy calculations and structure relaxation using density functional theory (DFT) using the measured parameters as input data. The relaxed crystal structure for each polytype was modelled to generate crystallographic information files (cif). STEM and electron diffraction simulations based on the crystallographic information data obtained from the DFT calculations show an excellent match to the empirical measurements. [ABSTRACT FROM AUTHOR]

Density functional theory (DFT) is used to obtain structural information of seven members of the tetradymite homologous series: Bi2Te3 (tellurobismuthite), BiTe (tsumoite), Bi4Te3 (pilsenite), Bi5Te3, Bi2Te, Bi7Te3 (hedleyite), and Bi8Te3. We use the formula S(Bi2kTe3)·L[Bi2(k+1)Te3] as a working model (k = 1–4) where S and L are short and long modules in the structures. The relaxed structures show an increase in the a parameter and decrease in the interlayer distance (dsub) from Bi2Te3 (2.029 Å) to Bi8Te3 (1.975 Å). DFT-derived formation energy for each phase indicates that they are all thermodynamically stable. Scanning transmission electron microscopy (STEM) simulations for each of the relaxed structures show an excellent match with atom models. Simulated electron diffractions and reflection modulation along c* are concordant with published data, where they exist, and with the theory underpinning mixed-layer compounds. Two modulation vectors, q = γ· c sub ∗ (γ = 1.800–1.640) and qF = γF· d sub ∗ (γF = 0.200–0.091), describe the distribution of reflections and their intensity variation along d sub ∗ = 1/dsub. The γF parameter reinforces the concept of Bi2kTe3 and Bi2(k+1)Te3 blocks in the double module structures, and γ relates to dsub variation. Our model describing the relationship between γ and dsub allows prediction of dsub beyond the compositional range considered in this study, showing that phases with k >5 have values dsub within the analytical range of interlayer distance in bismuth. This, in turn, allows us to constrain the tetradymite homologous series between γ values of 1.800 (Bi2Te3) and 1.588 (Bi14Te3). Phase compositions with higher Bi/Te should be considered as disordered alloys of bismuth. These results have implications for mineral systematics and classification as they underpin predictive models for all intermediate structures in the group and can be equally applied to other mixed-layer series. Our structural models will also assist in understanding variation in the thermoelectric and topological insulating properties of new compounds in the broader tetradymite group and can support experimental work targeting a refined phase diagram for the system Bi-Te. [ABSTRACT FROM AUTHOR]

An enrichment in nickel (Ni) or platinum group elements (PGE) is seldom observed in ores of the iron oxide–copper–gold (IOCG) type. This phenomenon is, however, known from a few deposits and prospects in the Carajás Mineral Province, Brazil. The Ni-PGE enrichment is explained, in part, by the spatial association of the IOCG-type ores with altered mafic-ultramafic lithologies, as well as by reworking and remobilization of pre-existing Ni and PGE during multiple mineralization and tectonothermal events across the Archean-Proterozoic. One such example of this mineralization is the Jatobá deposit in the southern copper belt of the Carajás Domain. This is the first detailed study of the Ni and PGE mineralization at Jatobá, with implications for understanding ore genesis. Petrographic and compositional study of sulfides shows that pyrite is the main Ni carrier, followed by pyrrhotite and exsolved pentlandite. Measurable concentrations of palladium (Pd) and platinum (Pt), albeit never more than a few ppm, are noted in pyrite. More importantly, however, the trace mineral signature of the Jatobá deposit features several platinum group minerals (PGM), including merenskyite, naldrettite, sudburyite, kotulskite, sperrylite, and borovskite. These PGM occur as sub-10 µm-sized grains that are largely restricted to fractures and grain boundaries in pyrite. All Pd minerals reported contain mobile elements such as Te, Bi, and Sb and are associated with rare earth- and U-minerals. This conspicuous mineralogy, differences in sulfide chemistry between the magnetite-hosted ore and stringer mineralization without magnetite, and microstructural control point to a genetic model for the sulfide mineralization at Jatobá and its relative enrichment in Ni and PGE. Observations support two alternative scenarios for ore genesis. In the first, an initial precipitation of disseminated or semi-massive Ni-PGE-bearing sulfides took place within the mafic rock pile, possibly in a VHMS-like setting. Later partial dissolution and remobilization of this pre-existing mineralization by mineralizing fluids of IOCG-type, possibly during the retrograde stage of a syn-deformational metamorphic event, led to their re-concentration within magnetite along structural conduits. The superposition of IOCG-style mineralization onto a pre-existing assemblage resulted in the observed replacement and overprinting in which PGE combined with components of the IOCG fluids like Sb, Bi, and Te. An alternative model involves leaching, by the IOCG-type fluids, of Ni and PGE from komatiites within the sequence or from ultramafic rocks in the basement. The discovery of PGM in Jatobá emphasizes the potential for additional discoveries of Ni-PGE-enriched ores elsewhere in the Carajás Domain and in analogous settings elsewhere. [ABSTRACT FROM AUTHOR]