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

Bi-Pb-chalcogenides of the aleksite series represent homologous mixed-layer compounds derived from tetradymite (Bi₂Te₂S). Considering tetradymite as composed of five-atom (Bi₂Te₂S) layers, the named minerals of the aleksite homologous series, aleksite (PbBi₂Te₂S₂) and saddlebackite, (Pb₂Bi₂Te₂S₃) have been considered as phases formed by regular stacking of longer seven- and nine-atom layers. High-angle annular dark-field scanning transmission electron microscope (HAADF-STEM) imaging of thinned foils prepared in-situ on domains deemed homogeneous from electron probe microanalysis, STEM energy-dispersive X-ray spectrometry (EDS) element mapping and fast Fourier transforms (FFTs) from the images offer new insights into these structures. The hitherto-unnamed phase, PbBi₄Te₄S₃, previously interpreted as regular intergrowths of five- and seven-atom layers, is characterized in terms of regular repeats of five- and seven-atom layers over distances of at least 350 nm, defining the (57), or 24H polytype. Imaging of other domains in the same lamella with identical composition at the electron microprobe scale reveals the presence of two additional polytypes: (5559), or 48H; and (557.559) or 72H. Unit cell dimensions for all three polytypes of PbBi₄Te₄S₃ can be both measured and predicted from the HAADF STEM imaging and FFTs. STEM EDS mapping of each polytype confirm the internal structure of each layer. Lead and S occur within the centre of the layers, i.e., Te–Bi–S–Pb–S–Bi–Te in the seven-atom layer, Te–Bi–S–Pb–S–Pb–S–Bi–Te in the nine-atom layer, and so on. Polytypism is an intrinsic feature of the aleksite series, with each named mineral or unnamed phase, except the simple five-atom layer, defined by several alternative stacking sequences of different length, readily explaining the differing c values given in previous work. Homology is defined in terms of layer width and the stacking arrangement of those layers. Coherent structures of the same composition need not only be built of layers of adjacent size (i.e., five- and seven-atom layers) but, as exemplified by the (5559) polytype, may also contain non-adjacent layers, a finding not anticipated in previous work. New polysomes remain to be discovered in nature and each potentially exists as multiple polytypes. The present study further emphasizes the utility of HAADF STEM imaging and atomic-scale STEM EDS element mapping as an optimal tool for tracking stacking sequences and characterising structures in mixed-layer compounds.

The supergiant Shuangjianzishan (SJS) Ag–Pb–Zn deposit, located in the southern Great Xing’an Range (SGXR), is the largest Ag deposit in China. The SJS deposit can be divided into two ore blocks: the Shuangjianzishan ore block and the Xinglongshan ore block. Given the importance of the Xinglongshan ore block in the SJS deposit, our work is focused on the Xinglongshan ore block. The vein orebodies in the Xionglongshan ore block mainly occur in the NW-, NNW-, and NNE-trending fault zones, and its mineralization is mainly related to a deep concealed syenogranite. Here, we present new geochronology, isotope geochemistry, and fluid inclusion data for the Xinglongshan ore block and provide additional insights into the metallogenic mechanism of the deposit. The dating results show that the syenogranite related to the mineralization formed at approximately 137 Ma, which is coherent with some previous age determinations in sulfides from the ore deposit. The mineralization of the Xinglongshan ore block can be divided into four stages: sphalerite–arsenopyrite–pyrite–chalcopyrite–quartz stage (stage I), sphalerite–galena–pyrite–silver-bearing mineral–quartz stage (stage II), sphalerite–galena–silver-bearing mineral–quartz–calcite stage (stage III), and weakly mineralized quartz–calcite stage (stage IV). Four types of fluid inclusions (FIs) have been identified within quartz and calcite veins: liquid-rich, gas-rich, pure-liquid, and pure-gas FIs. The homogenization temperatures in the four stages exhibit a gradual decrease, with stage I ranging from 253 to 302 °C, stage II from 203 to 268 °C, stage III from 184 to 222 °C, and stage IV from 153 to 198 °C, respectively. The salinity for stages I, II, III, and IV falls within the ranges of 3.4–6.6 wt% NaCl eqv., 2.6–7.2 wt% NaCl eqv., 2.9–7.0 wt% NaCl eqv., and 1.2–4.8 wt% NaCl eqv., respectively, indicative of a low-salinity ore-forming fluid. The δ¹⁸O_water and δD values of the ore-forming fluid span from −13.9‰ to 7.4‰ and −145‰ to −65‰, with δ¹³C_V-PDB values between −11.0‰ and −7.9‰. These values suggest that the ore-forming fluid predominantly originated from a mixture of magmatic and meteoric water. The ²⁰⁶Pb/²⁰⁴Pb, ²⁰⁷Pb/²⁰⁴Pb, and ²⁰⁸Pb/²⁰⁴Pb ratios of sulfides range from 18.278 to 18.361, 15.530 to 15.634, and 38.107 to 38.448, respectively. These ratios imply that the ore-forming material was primarily derived from the Early Cretaceous granitic magma, which resulted from the mixing of depleted mantle- and crustal-derived magmas. The fluid mixing was the dominant mechanism for mineral precipitation. The Xinglongshan ore block belongs to a magmatic-hydrothermal vein-type deposit related to the Early Cretaceous syenogranite, and the Shuangjianzishan ore block belongs to an intermediate sulfidation epithermal deposit related to coeval subvolcanic rocks. The Ag–Pb–Zn mineralization at Shuangjianzishan is genetically related to the Early Cretaceous volcanic–intrusive complex.

Selenium and Te are two important critical metals, which are often produced as by-products in Au-Cu deposits related to magmatic–hydrothermal systems, such as porphyry and skarn deposits. The Jilongshan Au-Cu deposit is a typical skarn deposit located in the middle and lower parts of the Yangtze River metallogenic belt. Previous studies show that it has valuable Se and Te resources, but their occurrence, particularly the relationship between the texture and composition of pyrite, and the enrichment mechanism of Se, Te, and Au remain unclear. Here, the textures and the major and trace elements of the Jilongshan pyrites were studied by using an optical microscope, EMPA, and LA-ICP-MS to reveal the occurrence of Se, Te, and Au in pyrite, as well as their genetic links with the pyrite mineralogical signature. The results show that there are three types of ores in the Jilongshan deposit, including granite porphyry-hosted, skarn-hosted, and carbonate-hosted ores. All of these ores contain major amounts of pyrite, which can be divided into four different generations. The first generation of pyrite (Py1) belongs to sedimentary genesis with a typical framboid texture and its Co/ Ni ratios are less than 1, whereas Py2, Py3, and Py4 belong to hydrothermal genesis and their Co/ Ni ratios are between 1.0 and 30.2. Selenium concentrations in Py2 and Py3 are relatively high (median, 138 ppm and 344 ppm, respectively), which are mainly present as isomorphism and a small amount as selenite in pyrite. Compared with granite porphyry-hosted and skarn-hosted ores, pyrite from carbonate-hosted ores has the highest Se concentrations. The latest generation of pyrite (Py4) contains the highest concentrations of Te (average, 140 ppm) and Au (average, 12 ppm) among the hydrothermal pyrites. Therefore, the precipitation of Se mainly occurs in pyrite during the early high-temperature stage, whereas higher concentrations of Te and Au are mainly enriched in pyrite during the late stage with low temperatures.