Clogauite, ideally PbBi4Te4S3 is the new n = 1 member of the aleksite series, PbnBi4Te4Sn+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$\bar{3}$m1, #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-12H, a = 4.277(4) Å, c = 23.46(14) Å, V = 371.598 Å3 and Z = 1; clogauite-24H, a = 4.278(4) Å, c = 46.88(31) Å, V = 743.053 Å3 and Z = 2; and clogauite-36H, 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.

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: n1 = 18 and n2 = 8 for tintinaite and n1 = 30 and n2 = 16 for izoklakeite. The homologue number can be calculated using the formula: N = (n1/6)–1 and N = n2/4 for PbS and SnS modules giving NTti = 2 and NIz = 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.

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

Health technology assessment (HTA) agencies vary in their use of quantitative patient preference data (PP) and the extent to which they have formalized this use in their guidelines. Based on the authors' knowledge of the literature, we identified six different PP “use cases” that integrate PP into HTA in five different ways: through endpoint selection, clinical benefit rating, predicting uptake, input into economic evaluation, and a means to weight all HTA criteria. Five types of insight are distinguished across the use cases: understanding what matters to patients, predicting patient choices, estimating the utility generated by treatment benefits, estimating the willingness to pay for treatment benefits, and informing distributional considerations. Summarizing the literature on these use cases, we recommend circumstances in which PP can add value to HTA and the further research and guidance that is required to support the integration of PP in HTA. Where HTA places more emphasis on clinical outcomes, novel endpoints are available; or where there are already many treatment options, PP can add value by helping decision makers to understand what matters to patients. Where uptake is uncertain, PP can be used to estimate uptake probability. Where indication-specific utility functions are required or where existing utility measures fail to capture the value of treatments, PP can be used to generate or supplement existing utility estimates. Where patients are paying out of pocket, PP can be used to estimate willingness to pay.

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

Pyrite is an ubiquitous constituent of the Proterozoic massive sulphide deposit at Deri, in the South Delhi Fold Belt of southern Rajasthan. Preserved pyrite microfabrics in the Zn-Pb-Cu sulphide ores of Deri reveal a polyphase growth history of the iron sulphide and enable the tectono-thermal evolution of the deposit to be reconstructed.

Primary sedimentary features in Deri pyrites are preserved as compositional banding. Regional metamorphism from mid-greenschist to low amphibolite facies is recorded by various microtextures of pyrite. Trails of fine grained pyrite inclusions within hornblende porphyroblasts define S1-schistosity. Pyrite boudins aligned parallel to S1 mark the brittle–ductile transformation of pyrite during the earliest deformation in the region. Isoclinal to tight folds (F1 and F2) in pyrite layers relate to a ductile deformation stage during progressive regional metamorphism. Peak metamorphic conditions around 550°C, an estimation supported by garnet–biotite thermometry, resulted in annealing of pyrite grains, while porphyroblastic growth of pyrite (up to 900 µm) took place along the retrogressive path. Brittle deformation of pyrite and growth of irregular pyritic mass around such fractured porphyroblasts characterize the waning phase of regional metamorphism. A subsequent phase of stress-free, thermal metamorphism is recorded in the decussate and rosette textures of arsenopyrite prisms replacing irregular pyritic mass. Annealing of such patchy pyrite provides information regarding the temperature conditions during this episode of thermal metamorphism which is consistent with the hornblendehornfels facies metamorphism interpreted from magnetite–ilmenite geothermometry (550°C) and sphalerite geobarometry (3.5 kbar). A mild cataclastic deformation during the penultimate phase produced microfaults in twinned arsenopyrite prisms.

The copper-bearing stratabound pyritic massive sulphide bodies contained in metamorphosed basic eruptives of Ordovician age at Sulitjelma in Nordland County, Norway, form one of the important fields of sulphide mineralisation within the Köli Nappe Complex. The sulphide bodies and their enclosing rocks were subject to successive stages of penetrative deformation and recrystallisation during the cycle of metamorphism and tectonic transport caused by the Scandian Orogeny. Textures within the ores and the immediate envelope of schists show that strain was focused along the mineralised horizons. The marked contrast in competence between the massive pyritic sulphides and their envelopes of alteration composed dominantly of phyllosilicates, and the metasediments of the overlying Furulund Group, led to the formation of macroscale fold and shear structures. On the mesoto microscale, a variety of textures have been formed within the pyrite-pyrrhotite-chalcopyrite-sphalerite sulphide rocks as a result of strain and recrystallisation. Variations in pyrite:pyrrhotite ratios and in the texture and proportions of associated gangue minerals evidently governed the strength and ductility of the sulphide rocks so that the same sulphide mineral can behave differently, displaying different textures in different matrices. In massive pyritic samples there is evidence of evolution towards textural equilibrium by recrystallisation, grain growth and annealment during the prograde part of the metamorphic cycle. Later, brittle deformation was superimposed on these early fabrics and the textural evidence is clearly preserved. By comparing published data on the brittle-ductile transformation boundaries of sulphide minerals with the conditions governing metamorphism at Sulitjelma, it is concluded that most of the brittle deformation in the sulphides took place during or after D3 under retrograde greenschist conditions. Grain growth of pyrite in matrices of more ductile sulphides during the prograde and early retrograde stages of metamorphism produced the coarse metablastic textures for which Sulitjelma is well-known. In some zones of high resolved shear stress, pyrite shows ductile behaviour which could be explained by a dislocation flow mechanism operating at conditions close to the metamorphic peak. In those horizons in which pyrrhotite is the dominant iron sulphide, the contrast in ductility between silicates, pyrite and pyrrhotite has led to the development of spectacular tectonoclastic textures in which fragments of wall rock have been broken, deformed, rolled and rotated within the ductile pyrrhotite matrix.

Several complex Cu-Pb-Bi, Cu-Pb-Bi-Sb and Ag-Pb-Bi sulphosalt minerals have been identified in samples from hydrothermal vein mineralisation associated with the Toroiaga sub-volcanic body in the Baia Borşa area of Maramureş County, northwest Romania. This is the first chemically-documented report of Bi-sulphosalts in the Neogene metallogenic province around Baia Mare. The investigated samples contain abundant amounts of matildite solid solution within galena, the Cu-Pb/Bi sulphosalts aikinite, friedrichite, krupkaite, hammarite, lindströmite and gladite as well as nuffieldite and berryite. Within the Ag-Pb/Bi group, the majority of analysed grains can be regarded as members of the lillianite homologous series. Three distinct lillianite homologues were identified, which correspond to (i) phases along the lillianite-gustavite solid solution join (Pb3Bi2S6-AgPbBi3S6), (ii) phases within solid solution field of heyrovskyite, and (iii) compositions which best correspond to ‘schirmerite’, sensu Makovicky and Karup-Møller (1977b), but may represent disordered gustavite, vikingite or eskimoite. Some of the analysed lillianite homologues contain excess Cu, which may occupy interstitial sites. Furthermore, a large proportion of the lillianite homologues display significant substitution of Sb for Bi within the limits predicted by experimental investigations. Cosalite, also showing a range of compositions including Sb-rich varieties is recognised. Izoklakeite, Cu2Pb22(Sb,Bi)22S57, is an abundant phase throughout the analysed samples, its composition is in good agreement with previously published analyses, except for excess Cu and Fe beyond the limits previously reported. The description of several minerals from this new occurrence and compositional data on them, including the Sb-bearing varieties, provides valuable additional information on compositional limits in natural samples.

The textural and paragenetic relationships of sulphide and sulphosalt minerals within Cu-Pb-Sb-Bi hydrothermal vein mineralization at the Apollo mine, Siegerland, Germany, are interpreted in terms of various reaction sequences. An earlier primary sulphide mineralization hosted within a siderite vein of the Siegerland type, with pyrite, chalcopyrite, sphalerite and galena as main component phases, has been overprinted by Sb-, Bi- and Cu-rich fluids. This superposition resulted in the formation of new quartz-stibnite veins, and various mineral reactions with the primary sulphides including the formation of the sulphosalt minerals semseyite, tetrahedrite, meneghinite, jaskolskiite, boulangerite, bournonite and zinkenite. Based on microprobe analyses of reaction pairs and determination of mineral proportions in some cases, a series of quantitative data for each mineral reaction may be generated. This, in turn, allows for the construction of isocon diagrams permitting the relative mobility and immobility of all chemical elements involved in each reaction to be discussed. Two stages of reactive replacement are identified, characterized by immobile behaviour of S and supply of Sb and Cu during the first stage and relative immobility of S and Sb with no further supply of metals during the second stage. Formation of sulphosalts inside the siderite vein during the first stage is interpreted as a decrease of disequilibrium between hydrothermal fluids and pre-existing vein minerals. Replacement processes of the second stage are interpreted as an equilibration of geochemical contrasts between different points within the siderite vein and also between the siderite and quartz-stibnite vein systems. The geochemical evolution of fluid composition during the entire mineralizing event may therefore be modelled, based on the transfer of chemical components reflected in the succession of mineral reactions. Such an approach has applications to comparable polyphase mineralization sequences, in which an understanding of fluid evolution patterns may greatly assist in the development of genetic models for mineral deposits. Solid-state diffusion and grain-boundary diffusion are considered to be the dominant mechanisms for short-range mass transport, whereas diffusion of ionic and complex species through the fluid is considered to be of major importance in long-range mass transport.

Concentration data are reported for 18 trace elements in chalcopyrite from a suite of 53 samples from 15 different ore deposits obtained by laser-ablation inductively-coupled plasma-mass spectrometry. Chalcopyrite is demonstrated to host a wide range of trace elements including Mn, Co, Zn, Ga, Se, Ag, Cd, In, Sn, Sb, Hg, Tl, Pb and Bi. The concentration of some of these elements can be high (hundreds to thousands of ppm) but most are typically tens to hundreds of ppm. The ability of chalcopyrite to host trace elements generally increases in the absence of other co-crystallizing sulfides. In deposits in which the sulfide assemblage recrystallized during syn-metamorphic deformation, the concentrations of Sn and Ga in chalcopyrite will generally increase in the presence of co-recrystallizing sphalerite and/or galena, suggesting that chalcopyrite is the preferred host at higher temperatures and/or pressures. Trace-element concentrations in chalcopyrite typically show little variation at the sample scale, yet there is potential for significant variation between samples from any individual deposit. The Zn:Cd ratio in chalcopyrite shows some evidence of a systematic variation across the dataset, which depends, at least in part, on temperature of crystallization. Under constant physiochemical conditions the Cd:Zn ratios in co-crystallizing chalcopyrite and sphalerite are typically approximately equal. Any distinct difference in the Cd:Zn ratios in the two minerals, and/or a non-constant Cd:Zn ratio in chalcopyrite, may be an indication of varying physiochemical conditions during crystallization.

Chalcopyrite is generally a poor host for most elements considered harmful or unwanted in the smelting of Cu, suggesting it is rarely a significant contributor to the overall content of such elements in copper concentrates. The exceptions are Se and Hg which may be sufficiently enriched in chalcopyrite to exceed statutory limits and thus incur monetary penalties from a smelter.