High-Entropy Pyrochlore A2B2O7 with Both Heavy and Light Rare-Earth Elements at the A Site

A novel class of high-entropy pyrochlore ceramics (HEPCs) with multiple heavy and light rare-earth elements at the A site were successfully synthesized via solid-state reaction. Both the XRD patterns and Raman spectroscopy demonstrated the single pyrochlore structure feature of seven kinds of HEPCs. Electron microscopic images revealed the typical morphology and the homogeneous distribution of all rare-earth elements. It can be concluded that the significance of configuration entropy in the HEPC system has promoted the tervalent lanthanide nuclides to form a single pyrochlore structure. This work is expected to provide guidance for the further design of high-entropy pyrochlore/fluorite ceramics.

Open-system behaviour of detrital zircon during weathering: an example from the Palaeoproterozoic Pretoria Group, South Africa

Detrital zircon in six surface samples of sandstone and contact metamorphic quartzite of the Magaliesberg and Rayton formations of the Pretoria Group (depositional age c. 2.20–2.06 Ga) show a major age fraction at 2.35–2.20 Ga, and minor early Palaeoproterozoic – Neoarchaean fractions. Trace-element concentrations vary widely, with Ti, Y and light rare earth elements (LREEs) spanning over three orders of magnitude. REE distribution patterns range from typical zircon patterns (LREE depletion, heavy REE enrichment, well-developed positive Ce and negative Eu anomalies) to patterns that are flat to concave downwards, with indistinct Ce and Eu anomalies. The change in REE pattern correlates with increases in alteration-sensitive parameters such as Ti concentration and (Dy/Sm) + (Dy/Nd), U–Pb discordance and content of common lead, and with a gradual washing-out of oscillatory zoning in cathodoluminescence images. U and Th concentrations also increase, but Th/U behaves erratically. Discordant zircon scatters along lead-loss lines to zero-age lower intercepts, suggesting that the isotopic and chemical variations are the results of disturbance long after deposition. The rocks sampled have been in a surface-near position (at least) since Late Cretaceous time, and exposed to deep weathering under intermittently hot and humid conditions. In this environment, even elements commonly considered as relatively insoluble could be mobilized locally, and taken up by radiation-damaged zircon. Such secondary alteration effects on U–Pb and trace elements can be expected in zircon in any ancient sedimentary rock that has been exposed to tropical–subtropical weathering, which needs to be considered when interpreting detrital zircon data.

SEIXOS DE FOSFATOS-SULFATOS DOS MINERAIS DO SUPERGRUPO ALUNITA NOS ALUVIÕES DIAMANTÍFEROS DE PAININN ÀS MARGENS DO TAPAJÓS EM ITAITUBA (PARÁ): GOYAZITA-FLORENCITA-GORCEIXITA-CRANDALLITA-ESVANBERGITA/WOODHOUSEITA

The diamond alluvium gravels from the Painin garimpos, on the right bank of the Tapajós River, in Itaituba, Pará, stand out for the marked presence of pebbles from <1 cm to about 10 cm in diameter consisting of aluminum phosphate-sulfates (APS minerals) from the alunite supergroup: goyazite-florencite-gorceixite-crandallite-esvanbergite/woodhouseite. They are light gray pebbles, still containing small amounts of pyrite, kaolinite, goethite and anatase. The total chemical and trace element analyzes confirm the indicated mineralogical constitution alongside the XRD. The florencite member is mainly dominated by Ce, La, Nd and Sm, the light rare earth elements, and also contains anomalous concentrations of Nb, Y, Pb, U and Th. This chemical nature of these pebbles, in part, makes it possible to compare them with the diamond satellite beans (favas) in secondary deposits in Brazil, but chemically only with the phosphates from Malawi and Sayan.

Age and Geochemistry of Late Jurassic Mafic Volcanic Rocks in the Northwestern Erguna Block, Northeast China

The northwestern Erguna Block, where a wide range of volcanic rocks are present, provides one of the foremost locations to investigate Mesozoic Paleo-Pacific and Mongol-Okhotsk subduction. The identification and study of Late Jurassic mafic volcanic rocks in the Badaguan area of northwestern Erguna is of particular significance for the investigation of volcanic magma sources and their compositional evolution. Detailed petrological, geochemical, and zircon U-Pb dating suggests that the Late Jurassic mafic volcanic rocks formed at 157–161 Ma. Furthermore, the geochemical signatures of these mafic volcanic rocks indicate that they are calc-alkaline or transitional series with weak peraluminous characteristics. The rocks have a strong MgO, Al2O3, and total alkali content, and a SiO2 content of 53.55–63.68 wt %; they are enriched in Rb, Th, U, K, and light rare-earth elements (LREE), and depleted in high-field-strength elements (HFSE), similar to igneous rocks in subduction zones. These characteristics indicate that the Late Jurassic mafic volcanic rocks in the Badaguan area may be derived from the partial melting of the lithospheric mantle as it was metasomatized by subduction-related fluid and the possible incorporation of some subducting sediments. Subsequently, the fractional crystallization of Fe and Ti oxides occurred during magmatic evolution. Combined with the regional geological data, it is inferred that the studied mafic volcanic rocks were formed by lithospheric extension after the closure of the Mongol-Okhotsk Ocean.

Structural and Compositional Features of Garnet-Containing Samples Synthesized in a System with Samarium at High Pressure and High Temperature

A distinctive feature of garnets associated with diamonds is specific containing of “light” rare earth elements. In the paper, the garnet-containing samples obtained at high pressure and high temperature in the system introduced with samarium (Sm) are studied. The experiments are carried out using a multianvil high-pressure apparatus of the “split-sphere” type (BARS) at a pressure of 5 GPa and a temperature of 1300 °С. The accuracy of measuring the pressure and temperature is ± 0.2 GPa и ± 25 °С, respectively. As a result, pyrope grains are synthesized with a CaO content no higher than 0.15 wt.% and Cr2O3 concentration within the range of 3.61-7.55 wt.%. The garnets are characterized by the stable presence of an impurity in the form of the Sm constituent. The garnets contain a significant amount of olivine inclusions. Crystals of the synthesized spinel are observed mainly in the interstices. This study demonstrates that the interaction of the components in the serpentine — chromite — corundum — Sm system leads to the crystallization of pyrope garnet, which forms large intergrowths of individual grains. The zoning observed in garnet is due to the transfer of components by fluid during the experiment. It is concluded that the Sm content in garnet can significantly increase depending on its content in the system.

A model involving amphibolite lower crust melting and subsequent melt extraction for leucogranite generation

In the southern Tibetan Plateau, leucogranites are dominantly distributed in the Himalayan orogenic belt with minor occurrences in the southern Lhasa subterrane. In this paper, we report the first Miocene Anglonggangri leucogranites in the northern Lhasa subterrane. This finding provides important constraints on both leucogranite petrogenesis and the tectono-magmatic evolution of the Lhasa terrane. The Anglonggangri leucogranites include biotite-muscovite granite and slightly younger garnet-muscovite granite and pegmatite. Zircon U-Pb and muscovite 40Ar-39Ar dating of these leucogranites yields Miocene ages of 11.1−10.2 Ma. The biotite-muscovite and garnet-muscovite granites are characterized by high SiO2 (72.3−74.4 wt%) and Al2O3 contents (14.4−15.4 wt%) and are peraluminous. The biotite-muscovite granite displays geochemical signatures with high Sr/Y (29.2−81.0) and (La/Yb)N (37.5−98.9) ratios, low Y (4.30−7.22 ppm) and Yb contents (0.26−0.47 ppm), low to moderate initial (87Sr/86Sr)i ratios (0.7085−0.7192), and moderate εNd(t) values (−10.17 to −6.94). Furthermore, they also exhibit radiogenic Pb isotope and variable zircon εHf(t) values (−9.6 to +4.4) with Proterozoic Nd (1.1−1.4 Ga) and Hf model ages (0.8−1.7 Ga). By comparison, the garnet-muscovite granite has lower CaO, MgO, TiO2, and total FeO contents and is enriched in Rb (380−466 ppm) and depleted in Sr (24.1−38.5 ppm) and Ba (30.7−58.6 ppm) and further characterized by a significant rare earth element (REE) tetrad effect and non-charge and radius-controlled (CHARAC) trace element behaviors. The garnet-muscovite granite shows a negative Eu anomaly and positive correlations among Sr and Eu, Sr and Ba, and Th and light rare earth elements (LREEs). Pegmatite comprising Nb-Ta oxides and cassiterite occurs in the garnet-muscovite granite. Geochronological and geochemical characteristics of the Anglonggangri leucogranites indicate that the magma of the biotite-muscovite granite was derived from partial melting of amphibolite lower crust contaminated with Proterozoic-Archean upper crustal materials. The garnet-muscovite granite was generated through melt extraction from the biotite-muscovite granite crystal mush. These results confirm that partial melting of the amphibolite lower crust not only occurred in the southern and central Lhasa subterranes but also in the northern Lhasa subterrane.

Arc-related peridotite blocks exhumed to the Eastern Block of the North China Craton prior to 2.47 Ga

The Songling and Majiayu peridotite blocks occur in the Eastern Block, North China Craton (NCC). Geothermobarometry data show that the Songling peridotites began exhumation from a depth of c. 70 km (c. 23 kbar). During exhumation, the Songling peridotites were intruded by an upper-crust-derived, high-δ18O (up to +7.28‰ in zircon) trondhjemitic dyke at 2.47 Ga and experienced granulite-facies metamorphism. The Songling peridotites have hybrid mantle wedge (HMW) -like high SiO2 (> 45 wt%), high FeOt (c. 10 wt%) content, high modal orthopyroxene abundance (> 35%) and high ϵNd(t) (+18.4 to +21.4), which were generated by the reaction between peridotite and eclogite-derived melts. The clinopyroxenes from the Songling peridotites were in equilibrium with a Nb-, Zr- and Ti-depleted arc-like magma. The Majiayu peridotites are characterized by depletion of Nb, Zr and Hf and are highly enriched in FeOt, Th and light rare earth elements (LREEs), which can be interpreted as an open system reaction between hydrous melts and fore-arc mantle peridotites. These two peridotite blocks are considered to be arc-related mantle peridotites that experienced melt extraction and metasomatism in different styles. They were exhumed to the north margin of the North China Craton during the c. 2.47 Ga arc–continent collision along the Zunhua structural belt.

Li-Co–Ni-Mn-(REE) veins of the Western Erzgebirge, Germany—a potential source of battery raw materials

Situated in the western Erzgebirge metallogenetic province (Vogtland, Germany), the Eichigt prospect is associated with several quartz-Mn-Fe-oxyhydroxide veins that are exposed at surface. Bulk-rock geochemical assays of vein material yield high concentrations of Li (0.6–4.1 kg/t), Co (0.6–14.7 kg/t), and Ni (0.2–2.8 kg/t), as well as significant quantities of Mn, Cu, and light rare earth elements, a very unusual metal tenor closely resembling the mixture of raw materials needed for Li-ion battery production. This study reports on the results of a first detailed investigation of this rather unique polymetallic mineralization style, including detailed petrographic and mineralogical studies complemented by bulk rock geochemistry, electron microprobe analyses, and laser ablation inductively coupled mass spectrometry. The mineralized material comprises an oxide assemblage of goethite hematite, hollandite, and lithiophorite that together cement angular fragments of vein quartz. Lithiophorite is the predominant host of Li (3.6–11.1 kg/t), Co (2.5–54.5 kg/t), and Ni (0.2–8.9 kg/t); Cu is contained in similar amounts in hollandite and lithiophorite whereas light rare earth elements (LREE) are mainly hosted in microcrystalline rhabdophane and florencite, which are finely intergrown with the Mn-Fe-oxyhydroxides. 40Ar/39Ar ages (~ 40–34 Ma) of coronadite group minerals coincide with tectonic activity related to the Cenozoic Eger Graben rifting. A low-temperature hydrothermal overprint of pre-existing base metal sulfide-quartz mineralization on fault structures that were reactivated during continental rifting is proposed as the most likely origin of the polymetallic oxyhydroxide mineralization at Eichigt. However, tectonically enhanced deep-reaching fracture-controlled supergene weathering cannot be completely ruled out as the origin of the mineralization.