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Xenotime-(Gd), ideally GdPO4, is a new mineral of the xenotime group. It was discovered at the Zimná Voda REE–U–Au occurrence near Prakovce, Western Carpathians, Slovakia. It forms rare crystal domains (≤20 μm, usually ≤10 μm in size) in Gd-rich xenotime-(Y) crystals (≤100 μm in size), in association with monazite-group minerals, uraninite, fluorapatite and uranyl arsenates–phosphates. The hydrothermal REE–U–Au mineralisation occurs in a quartz–muscovite vein, hosted in Palaeozoic phyllites near exocontact with Permian granites. The density is 5.26 g/cm3, based on calculated average empirical formula and unit-cell parameters. The average chemical composition (n = 6) measured by electron microprobe is as follows (wt.%): P2O5 30.1, As2O5 0.5, SiO2 0.2, UO2 0.3, Y2O3 15.7, (La, Ce, Pr, Nd)2O3 0.5, Sm2O3 5.7, Eu2O3 1.4, Gd2O3 29.2, Tb2O3 3.9, Dy2O3 10.4, Ho2O3 0.4, (Er, Tm, Yb, Lu)2O3 2.1, (Ca, Fe, Pb, Mn, Ba)O 0.1, total 100.5. The corresponding empirical formula calculated on the basis of 4 oxygen atoms is: (Gd0.37Y0.32Dy0.13Sm0.08Tb0.05Eu0.02Er0.01Tm0.01Nd0.01...)Σ1.01(P0.98As0.01Si0.01)O4. The empirical formula of the Gd-richest composition is: (Gd0.38Y0.31Dy0.13Sm0.08Tb0.05Eu0.02Er0.01Nd0.01Ho0.01...)Σ1.01(P0.98As0.01Si0.01)O4. The ideal formula is GdPO4. The xenotime-type structure has been confirmed by micro-Raman spectroscopy and a Fast Fourier-Transform pattern using HRTEM. Xenotime-(Gd) is tetragonal, space group I 41/ amd , a = 6.9589(5) Å, c = 6.0518(6) Å, V = 293.07(3) Å3 and Z = 4. The new mineral is named as an analogue of xenotime-(Y) and xenotime-(Yb) with Gd dominant among the REE. The middle REE enrichment of xenotime-(Gd) is shared with the associated monazite-(Gd) and Gd-rich hingganite-(Y). This exotic REE signature and precipitation of Gd-bearing minerals is a product of selective complexing and enrichment in MREE in low-temperature hydrothermal fluids by alteration of uraninite, brannerite and fluorapatite on a micro-scale. The existence of xenotime-(Gd) and monazite-(Gd) is the first naturally documented dimorphism among REE phosphates. In addition, xenotime-(Gd) is only the third approved Gd-dominant mineral, after lepersonnite-(Gd) and monazite-(Gd). [ABSTRACT FROM AUTHOR]

A hydrothermal quartz vein with REE-U-Au mineralization in the Zimná Voda (Gemeric Unit, Western Carpathians, Slovakia) is associated with contact metamorphism between Permian granites and host phyllites and metaquartzites. It contains unique REE minerals of the monazite and xenotime groups. Monazite-(Ce), monazite-(Nd), monazite-(Sm), and Gd-dominant monazite ["monazite-(Gd)"], along with xenotime-(Y) to Gd-dominant xenotime ["xenotime-(Gd)"] and Gd-rich hingganite-(Y) show heterogeneous compositions and reflect a strong fractionation trend toward the enrichment of MREE (Sm to Dy), particularly Gd. Here, the gadolinium abundance reported in "monazite-(Gd)" (≤23.4 wt% Gd2O3) and Gd-rich xenotime-(Y) to "xenotime-(Gd)" (≤28.7 wt% Gd2O3) and accompanied by Gd-rich hingganite-(Y) (≤15.8 wt% Gd2O3), is among the highest Gd concentrations ever reported in natural minerals. The Gd-richest compositions show the following formulas: (Gd0.31Sm0.24 Nd0.15Ce0.10La0.05Dy0.03Y0.03...)0.98PO4 ["monazite-(Gd)"], (Gd0.36Y0.32Dy0.13Sm0.08Tb0.05...)0.98 (P0.96As0.04)1.00O4 ["xenotime-(Gd)"] and (Y0.71Gd0.43Dy0.23Sm0.22Tb0.06Er0.04Nd0.06...Ca0.06)1.96 ( ◻ 0.87 Fe 0.13 2 +) 1.00 (B e 1.82 B 0.18 ) 2.00 (S i 1.90 A s 0.10 ) 2.00 O 8 (O H 1.70 O 0.30 ) 2.00 [hingganite-(Y)]. The MREE-rich monazites, xenotimes, and hingganite-(Y) precipitated in response to the alteration of primary uraninite, brannerite, and fluorapatite by low-temperature hydrothermal fluids of heterogeneous compositions on a microscale. These are responsible for the strong enrichment of individual MREE, especially Gd in the secondary minerals. This is accompanied by the advancing development of the W-type tetrad effect on REE through monazite species. The substantial incorporation of Gd into both REE-selective monazite and xenotime structures that are accompanied by LREE vs. HREE segregation indicates the possibility of differently sized REE3+ miscibility in REEPO4 solid solutions, as well as the stabilization of the Gd-rich orthophosphate structure by substitution of the remaining A-site cations with smaller HREE+Y in the xenotime-type, and/or larger LREE in the monazite-type structure. [ABSTRACT FROM AUTHOR]

An assemblage of alunite-supergroup minerals (ASM), rhabdophane-group minerals (RGM), goethite and associated clay minerals occurs in Permian A-type porphyritic microgranite in the eastern part of the Velence Hills, Hungary. The secondary sulfates/phosphates include jarosite, Pb-rich jarosite and alunite, corkite, hinsdalite and rhabdophane-(Ce), -(La) and -(Nd). Detailed electron probe microanalysis and Raman spectroscopy reveal a wide miscibility among RGM end-members and show a rhabdophane–tristramite–brockite solid solution with extensive compositional variation. Moreover, ASM show heterogeneous composition and complex substitution mechanisms within the alunite, beudantite and plumbogummite groups. The formation of this rare mineral assemblage reveals extensive remobilization of rare-earth elements (REE), Th, U, P, S, Fe and Pb under supergene conditions. Compositional variations and substitution trends of the RGM investigated indicate that Th, U, Ca and Pb are incorporated into the rhabdophane structure by a (Ca, Pb)2+ + (Th, U)4+ ↔ 2 REE 3+ substitution mechanism. Consequently, we suggest the following end-member formulae for RGM containing divalent and tetravalent cations: (Ca0.5Th0.5)PO4·H2O for brockite, (Pb0.5Th0.5)PO4·H2O for grayite and (Ca0.5U0.5)PO4·2H2O for tristramite. The ASM and RGM originated from total leaching of the primary magmatic REE , Th, U and P minerals in the microgranite [most probably allanite-(Ce), fluorapatite and possibly also xenotime-(Y)], together with input of Pb and S in low-temperature, acid sulfate solutions, connected with an adjacent Palaeogene andesite–diorite intrusion and the accompanying hydrothermal sulfide mineralization. [ABSTRACT FROM AUTHOR]

In talc-magnesite veins in serpentinite near Muránska Dlhá Lúka (MDL), Slovakia, yellow euhedral to subhedral crystals apatite of a gem quality occur. It has a composition of hydroxylapatite with F− varying between 0.29 and 0.34 apfu, Cl− in range of 0.02–0.05 apfu and calculated OH− content between 0.62–0.68 apfu. Moreover, [CO3]2− molecules were identified by FTIR and Raman spectroscopy. MDL apatite contains only up to 0.003 apfu As5+ and Si4+ substituting for P5+; Ca is substituted by small amount of Na, Fe2+, Mn2+ (all up to 0.006 apfu), and Rare Earth Elements (REE—in total up to 0.017 apfu). Compared to trace-element composition of similar apatites from Durango, Mexico, the REE content in MDL apatite is around ten times lower with Nd > Ce >> La, its chondrite-normalized REE pattern has almost a horizontal slope and larger negative Eu anomaly. The MDL apatite is richer in Mn, Pb and Li, but poorer in As, V, Th and U. The concentrations of Sr and Y are similar. In the optical absorption spectra, the most prominent bands are at 585–590 nm (Nd3+) and between 600 and 800 nm (Mn2+, Ce3+-SiO3− photochromic center and Nd3+). The photoluminescence spectrum of MDL apatite shows bands between 550 and 620 nm (Dy3+, Sm3+, Pr3+ and also Mn2+) which likely enhance its yellow color. MDL hydroxylapatite likely formed from fluids derived from granitic rocks as evidenced by the chondrite-normalized REE patterns, Li, Mn and Y concentrations. The Sr content reflects the host-rock serpentinite composition. Fluids for its crystallization were likely derived from Muráň complex orthogneisses by the Alpine deformation and recrystallization in greenschist to lower amphibolite facies. [ABSTRACT FROM AUTHOR]

The site preference for each cation and site in beryl based on bond-length calculations was determined and compared with analytical data. Tetrahedral SiO4 six-membered rings normally have no substitutions which results from very compact Si4+–O bonds in tetrahedra. Any substitution except Be would require significant tetrahedral ring distortion. The Be tetrahedron should also be negligibly substituted based on the bond-valence calculation; the tetrahedral Li–O bond length is almost 20% larger than Be2+–O. Similar or smaller bond lengths were calculated for Cr3+, V3+, Fe3+, Fe2+, Mn3+, Mg2+, and Al3+, which can substitute for Be but also can occupy a neighboring tetrahedrally coordinated site which is completely vacant in the full Be occupancy. The octahedral site is also very compressed due to dominant Al with short bond lengths; any substitution results in octahedron expansion. There are two channel sites in beryl: the smaller 2b site can be occupied by Na+, Ca2+, Li+, and REE3+ (Rare Earth Elements); Fe2+ and Fe3+ are too small; K+, Cs+, Rb+, and Ba2+ are too large. The channel 2a-site average bond length is 3.38 Å which allows the presence of simple molecules such as H2O, CO2, or NH4 and the large-sized cations-preferring Cs+. [ABSTRACT FROM AUTHOR]

Monazite-(Gd), ideally GdPO4, is a new mineral of the monazite group. It was discovered near Prakovce-Zimná Voda, ~23 km WNW of Košice, Western Carpathians, Slovakia. It forms anhedral domains (≤100 μm, mostly 10–50 μm in size), in close association with monazite-(Sm), Gd-bearing xenotime-(Y), Gd-bearing hingganite-(Y), fluorapatite and uraninite. All these minerals are hosted in a REE–U–Au quartz–muscovite vein, hosted in phyllites in an exocontact to granites. The density calculated using the average empirical formula and unit-cell parameters is 5.55 g/cm3. The average chemical composition measured by means of electron microprobe is as follows (wt.%): P2O5 29.68, As2O5 0.15, SiO2 0.07, ThO2 0.01, UO2 0.04, Y2O3 1.30, La2O3 3.19, Ce2O3 6.93, Pr2O3 1.12, Nd2O3 10.56, Sm2O3 17.36, Eu2O3 1.49, Gd2O3 22.84, Tb2O3 1.57, Dy2O3 2.27, CaO 0.21, total 99.67. The corresponding empirical formula calculated on the basis of 4 oxygen atoms is: (Gd0.30Sm0.24Nd0.15Ce0.10La0.05Dy0.03Y0.03Tb0.02Eu0.02Pr0.02Ca0.01)0.98P1.01O4. The ideal formula is GdPO4. The monazite-type structure has been confirmed by micro-Raman spectroscopy and selected-area electron diffraction. Monazite-(Gd) is monoclinic, space group P 21/ n , a = 6.703(1) Å, b = 6.914(1) Å, c = 6.383(1) Å, β = 103.8(1)°, V = 287.3(1) Å3 and Z = 4. The middle REE enrichment of monazite-(Gd) is shared with the associated Gd-bearing xenotime-(Y) to 'xenotime-(Gd)' and Gd-bearing hingganite-(Y). This exotic REE signature and precipitation of Gd-bearing mineral assemblage is a product of selective complexing and enrichment in middle REE in low-temperature hydrothermal fluids by alteration of primary uraninite, brannerite and fluorapatite on a micro-scale. The new mineral is named as an analogue of monazite-(La), monazite-(Ce), monazite-(Nd) and monazite-(Sm) but with Gd dominant among the REE. [ABSTRACT FROM AUTHOR]

Two contrasting reaction coronae were developed around rare earth element (REE) accessory phosphates in Variscan metagranitic rocks, which have been overprinted by Alpine blastomylonitisation from the Fabova Hol'a Massif, in the Veporic Unit, Western Carpathians, Central Slovakia. The Th–U–Pb total EPMA age determination of primary magmatic monazite-(Ce) from the metagranite indicates a Carboniferous (Mississippian, Tournaisian) age of 355 ± 1.9 Ma. Monazite-(Ce) breakdown resulted in impressive, though common, fluorapatite ± Th-silicate + allanite-(Ce) + clinozoisite coronae. The alteration of xenotime-(Y) produced a novel type of secondary coronal micro-texture consisting of a massive fluorapatite mantle zone and tiny satellite crystals of hellandite-(Y) [(Ca,REE)4Y2Al□2(B4Si4O22)(OH)2] and hingganite-(Y) [Y2□Be2Si2O8(OH)2] of ~1–5 μm, and rarely ≤10 μm in size. The localised occurrence of Y–B–Be silicates, which are associated closely with other secondary minerals, suggests the involvement of B and Be during the metasomatic alteration transformation of xenotime-(Y). General reactions for monazite-(Ce) and xenotime-(Y) decomposition, including the fluids involved, can be written as follows: Mnz + (Ca, Fe, Si, Al and F)-rich fluid → FAp + Ht + Aln + Czo; Xtm + (Ca, Fe, Si, Al, F, B and Be)-rich fluid → FAp + Hld + Hin + Czo. The granitic rocks underwent Early Cretaceous burial metamorphism under greenschist- to lower amphibolite-facies P–T conditions. Subsequently, Alpine post-collisional uplift and exhumation of the Veporic Unit, starting from the Late Cretaceous epoch, was accompanied by a retrograde tectono-metamorphic overprint; the activity of external fluids, caused the formation of secondary coronae minerals around monazite-(Ce) and xenotime-(Y). A portion of B (± Be) should have been liberated from the metagranite feldspars, micas, or xenotime-(Y) enriched in (Nb,Ta)BO4 (schiavinatoite or béhierite) components. However, the principal source of B and Be in fluids necessary for the production of hellandite and hingganite, was probably of external origin from adjacent magmatic, metamorphic, or sedimentary rocks (Permian granites, rhyolites and sedimentary rocks, and Palaeozoic metapelites). [ABSTRACT FROM AUTHOR]