Evolution of Nb–Ta Oxide Minerals and Their Relationship to the Magmatic-Hydrothermal Processes of the Nb–Ta Mineralized Syenitic Dikes in the Panxi Region, SW China

Previous geochemical and petrological studies have concluded that initially magmatic Nb–Ta mineralization is often modified by post-magmatic hydrothermal fluids; however, there is still a lack of mineralogical evidence for the syenite-related Nb–Ta deposit. From the perspective of Nb–Ta minerals, the pyrochlore supergroup minerals have significance for indicating the fluid evolution of alkaline rock or related carbonatite type Nb–Ta deposits. The Panzhihua–Xichang (Panxi) region is a famous polymetallic metallogenic belt in southwestern China, abound with a huge amount of Nb–Ta mineralized syenitic dikes. This study focuses on the mineral textures and chemical compositions of the main Nb–Ta oxide minerals (including columbite-(Fe), fersmite, fergusonite-(Y), and especially pyrochlore group minerals) in samples from the Baicao and Xiaoheiqing deposits, in the Huili area, Panxi region, to reveal the magma evolution process of syenitic-dike-related Nb–Ta deposits. The Nb–Ta oxides in the Huili syenites are commonly characterized by a specific two-stage texture on the crystal scale, exhibiting a complex metasomatic structure and compositional zoning. Four types of pyrochlore group minerals (pyrochlores I, II, III, and IV) formed in different stages were identified. The euhedral columbite-(Fe), fersmite, and pyrochlores I and II minerals formed in the magmatic fractional crystallization stage. Anhedral pyrochlore III minerals are linked to the activity of magma-derived hydrothermal fluids at the late stages of magma evolution. The pyrochlore IV minerals and fergusonite-(Y) tend to be more concentrated in areas that have undergone strong albitization, which is a typical phenomenon of hydrothermal alteration. These mineralogical phenomena provide strong evidences that the magmatic-hydrothermal transitional stage is the favored model for explaining the Nb–Ta mineralization process. It is also concluded that the changes in chemical composition and texture characteristics for pyrochlore group minerals could serve as a proxy for syenite-related Nb–Ta mineralization processes.

Hydroxykenopyrochlore, (□,Ce,Ba)2(Nb,Ti)2O6(OH,F), a New Member of the Pyrochlore Group from Araxá, Minas Gerais, Brazil

ABSTRACT Hydroxykenopyrochlore, (□,Ce,Ba)2(Nb,Ti)2O6(OH,F), occurs in a weathered Nb-ore from alkaline-carbonatite complexes and pegmatites of the Brazilian shield mined by Compania Brasileira de Metalurgia e Mineração (CBMM), Araxá, Minas Gerais, Brazil. The mineral is a product of alkali metasomatism. It occurs as parts of granular grains up to 0.1 mm in size in association with Ba-bearing hydrokenopyrochlore. Hydroxykenopyrochlore is lemon yellow to yellow in color, non-fluorescent, and brittle. The hardness is 4½ on the Mohs scale. The calculated density is 4.36 g/cm3. It is cubic, Fd–3m, with cell parameters a 10.590(5) Å, V = 1187.6(10) Å3, and Z = 2. The strongest seven lines in the powder XRD pattern [d in Å (I/I0) hkl] are 6.06 (49) 111, 3.18 (27) 311, 3.05 (100) 222, 2.64 (29) 400, 1.870 (56) 440, 1.594 (50) 622, 1.213 (15) 662, and 1.182 (13) 840. The empirical formula derived from electron-microprobe analyses is [□1.117Ce0.532Nd0.035La0.021Pr0.010Sm0.003Y0.002Ba0.101Ca0.030Pb0.004Th0.061U0.007K0.040Na0.036]Σ2(Nb1.368Ti0.325P0.095Fe0.091Al0.082Zr0.039)Σ2[O4.719(OH)1.281]Σ6[(OH)0.846F0.154]. Hydroxykenopyrochlore is a member of the pyrochlore supergroup (class 4.DH.15 of Strunz & Nickel; class 8.2.1. of Dana). It is the vacancy-dominant analogue of hydroxycalciopyrochlore, (Ca,Na,U,□)2(Nb,Ti)2O6(OH), and the Nb-dominant analogue of hydroxykenomicrolite, (□,Na,Sb3+)2Ta2O6(OH), and of hydroxykenoelsmoreite, (□,Pb)2(W,Fe3+,Al)2(O,OH)6(OH).

Cesiokenopyrochlore, the First Natural Niobate with an Inverse Pyrochlore Structure

Cesiokenopyrochlore is a new mineral belonging to the pyrochlore group. It was discovered in a specimen of granitic pegmatite collected at Tetezantsio, Betafo region, Madagascar. The mineral forms rough equant crystals up to 0.05 mm in size intergrown with béhierite and rynersonite. Cesiokenopyrochlore is light-brown, translucent, with resinous luster. Dcalc. = 5.984 g/cm3. In reflected light it is light gray, isotropic, with strong light-brown internal reflections. The crystal structure was refined to R1 = 0.0212. The mineral is cubic, , a = 10.444(1) Å, V = 1139.5(2) Å3, and Z = 8. The strongest lines of the powder X-ray diffraction pattern [d, Å, (I, %) (hkl)] are: 6.03 (37) (111), 3.70 (9) (220), 3.15 (100) (311), 3.02 (36) (222), 2.012 (17) (511, 333), 1.848 (19) (440), 1.576 (11) (622). The chemical composition is (wt.%; electron microprobe): Cs2O 22.66, Na2O 1.74, CaO 0.64, Nb2O5 20.87, Ta2O5 21.27, WO3 30.67, H2O (calc) 0.12, total 97.97. The empirical formula of the holotype specimen calculated on the basis of (Nb+Ta+W) = 2 apfu and (O+OH) = 6 apfu and written according to the pyrochlore-supergroup nomenclature is Na0.29Ca0.06(Nb0.81W0.69Ta0.50)Σ2[O5.93(OH)0.07]Σ6Cs0.83. The simplified formula of the holotype specimen is □2(Nb,W,Ta)Σ2O6Cs. Cesiokenopyrochlore is the first natural niobate to adopt the inverse pyrochlore structure.

Natural blue zircon from Vesuvius

Zircon from syenitic ejecta of Vesuvius (Campania, Italy) is unusually blue, a property shared with gem zircon from Ratanakiri province (Cambodia), which turns from natural reddish-brown to blue when heated under reducing conditions. Here, the origins of these unusual crystals were traced through geochronology, trace elements, and O-Hf isotopic compositions. The causes of its colour were investigated through optical and electron microscopy, optical absorption spectroscopy, and Raman microspectroscopy. Colour stability upon heating and ultraviolet light (UV) exposure was tested using Ratanakiri zircon as a control. Vesuvius zircon contains vesiculated zones with abundant inclusions ~2.5 μm to <100 nm in diameter (mostly U-rich thorianite and pyrochlore-group minerals), while homogeneous zircon domains are high in Th and U (up to 5.9 and 1.8 wt%, respectively). Its blue colouration is stable under UV radiation, as well as heat-treatment under reducing conditions (1000 °C; >15 h). Turbid domains rich in large inclusions change to yellow-brown after heating under oxidizing conditions, while transparent domains remain pale blue or colourless. Optical absorption spectra display sharp absorption lines attributed to U4+, and slightly elevated absorption towards shorter wavelengths. The ~1007 cm−1 ν3(SiO4) Raman band is broadened due to lattice distortion by non-stoichiometric elements in high-Th/-U zircon, whereas narrow bands in inclusion-rich domains indicate a decrease in lattice strain due to inclusion precipitation. Blue colouration in Vesuvius zircon is explained by the effect of light scattering (Rayleigh and/or Mie scattering) on highly refractive actinide-rich inclusions ranging in size from <1/10 to few multiples of the wavelengths of visible light. Inclusions likely formed during fluid-mediated coupled dissolution-reprecipitation that locally transformed lattice-strained actinide-rich zircon within several hundreds of years prior to eruption.

Hydroxyplumbopyrochlore, (Pb1.5,□0.5)Nb2O6(OH), a new member of the pyrochlore group from Jabal Sayid, Saudi Arabia

ABSTRACTA new mineral species of the pyrochlore supergroup, hydroxyplumbopyrochlore (IMA2018-145), (Pb1.5,□0.5)Nb2O6(OH), has been discovered in the Jabal Sayid peralkaline granitic complex of the Arabian Shield, Saudi Arabia. It is associated with quartz, microcline, ‘biotite’, rutile, zircon, calcite, rhodochrosite, columbite-(Fe), goethite, thorite, bastnäsite-(Ce), xenotime-(Y), samarskite-(Y), euxenite-(Y), hydropyrochlore and fluornatropyrochlore. Hydroxyplumbopyrochlore usually shows euhedral octahedra, slightly rhombic dodecahedra and cubes or their combination (0.01–0.06 mm). The mineral is pale yellow to pale brown, transparent with white streak, and has adamantine to transparent lustre. It is brittle with conchoidal fracture. No cleavage or parting are observed. It is isotropic and non-fluorescent. The average microhardness is 463.4 kg mm–2. The calculated density is 6.474 g cm–3.Hydroxyplumbopyrochlore belongs to the cubic crystal system and exhibits the space group Fd$\bar{3}$m with unit-cell parameters a = 10.5456(6) Å, V = 1172.8(2) Å3 and Z = 8. Electron microprobe analysis gave (6-point average composition, wt.%): CaO 0.32, SrO 0.16, FeO 0.17, Ce2O3 0.07, Pr2O3 0.02, PbO 51.69, Nb2O5 40.06, SiO2 0.05, TiO2 1.68, Ta2O5 4.74, H2Ocalc 0.95, total 99.90, yielding the empirical formula (Pb1.34Ca0.03Fe0.01Sr0.01□0.61)Σ2(Nb1.75Ti0.12Ta0.12Si0.01)Σ2O6(OH0.53O0.08□0.39)Σ1, where □ = vacancy. The Raman spectrum of hydroxyplumbopyrochlore contains the characteristic bands of O–H vibrations and no bands for H2O vibrations.

Silicate-Carbonate Liquid Immiscibility: Insights from the Crevier Alkaline Intrusion (Quebec)

This contribution explores the petrogenetic relationships between silicate and carbonatitic rocks in the Crevier Alkaline Intrusion (CAI, Québec, Canada). The CAI is located in the Proterozoic Grenville Province and is composed of a suite of undersaturated peralkaline rocks from ijolite to nepheline syenite and carbonatites. Petrogenetic relationships between different undersaturated alkaline igneous rocks, carbonate-bearing and carbonate-free nepheline syenite and carbonatites observed in the CAI suggest that (1) carbonate-bearing and carbonate-free silicate rocks are comagmatic with carbonatite, and that (2) both silicate and carbonatitic liquids are fractionated from an ijolitic parental magma that has undergone liquid immiscibility. One of the observed facies is characterized by spectacular ocelli of carbonate-bearing nepheline syenite in a matrix of carbonatite. The younger nepheline syenite facies can be divided into two groups based on the presence or absence of magmatic carbonates. Both groups are characterized by the presence of pyrochlore-group minerals that carry the Nb–Ta mineralization. We specifically use accessory minerals such as zircon, pyrochlore and apatite to constrain the temporal and physicochemical parameters of the immiscibility process. By coupling (1) mineral textures, (2) trace elements, (3) Ti-in-zircon thermometry, and (4) oxygen isotope compositions, we have traced the crystallization of zircon before, during and after the immiscibility process. The results allowed us to constrain the minimum temperature of this process at ∼815–865°C. In addition, two magmatic populations of pyrochlore are identified through their petrographic and geochemical characteristics within the younger nepheline syenite facies. Pyrochlore from the earlier ocelli facies of carbonate-bearing nepheline syenite follow a Nb–Ta differentiation trend, whereas pyrochlore from the younger carbonate-free nepheline syenite follow a more classical Nb–Ti trend. Following the complete immiscibility between the silicate and carbonatitic liquids, the fractionation between Nb and Ta stopped while a new generation of Nb-rich pyrochlore grew, displaying a more classical Nb–Ti fractionation trend and a higher Nb/Ta ratio in the nepheline syenite.

Pyrochlore-Group Minerals in the Granite-Hosted Katugin Rare-Metal Deposit, Transbaikalia, Russia

Pyrochlore group minerals are the main raw phases in granitic rocks of the Katugin complex-ore deposit that stores Nb, Ta, Y, REE, U, Th, Zr, and cryolite. There are three main types: Primary magmatic, early postmagmatic (secondary-I), and late hydrothermal (secondary-II) pyrochlores. The primary magmatic phase is fluornatropyrochlore, which has high concentrations of Na2O (to 10.5 wt.%), F (to 5.4 wt.%), and REE2O3 (to 17.3 wt.%) but also low CaO (0.6–4.3 wt.%), UO2 (to 2.6 wt.%), ThO2 (to 1.8 wt.%), and PbO (to 1.4 wt.%). Pyrochlore of this type is very rare in nature and is limited to a few occurrences: Rare-metal deposits of Nechalacho in syenite and nepheline syenite (Canada) and Mariupol in nepheline syenite (Ukraine). It may have crystallized synchronously with or slightly later than melanocratic minerals (aegirine, biotite, and arfvedsonite) at the late magmatic stage when Fe from the melt became bound, which hindered the crystallization of columbite. Secondary-I pyrochlore follows cracks or replaces primary pyrochlore in grain rims and is compositionally similar to the early phase, except for lower Na2O concentrations (2.8 wt.%), relatively low F (4 wt.%), and less complete A- and Y-sites occupancy. Secondary-II pyrochlore is a product of late hydrothermal alteration, which postdated the formation of the Katugin deposit. It differs in large ranges of elements and contains minor K, Ba, Pb, Fe, and significant Si concentrations but also low Na and F. Its composition mostly falls within the field of hydro- and keno-pyrochlore.