Chromium mineralization in the Khibiny alkaline massif (Kola Peninsula,Russia)

This paper presents new data on chromium mineralization in a fenitized xenolith in Mt. Kaskasnyunchorr in the Khibiny alkaline massif (Kola Peninsula, Russia) and summarizes data on Cr mineralogy in the Khibiny Mountains. Protolith silicates that contained Cr³⁺ admixture are believed to be the source of this element in the fenite. Cr-bearing (maximum Cr₂O₃ concentrations, wt %, are in parentheses) aegirine (5.8), crichtonite-group minerals (2.1), muscovite (1.3), zirconolite (1.1), titanite (1.0), fluorine-magnesioarfvedsonite (0.8), biotite (0.8), ilmenite (0.6), and aenigmatite (0.6) occur in the fenite. The late-stage spinellides of the FeTi-chromite-CrTi-magnetite series, which are very poor in Mg and Al and which formed after Crrich aegirine and ilmenite, are the richest in Cr (up to 42% Ct₂O₃). Cr concentrations grew with time during the fenitization process. Unlike minerals in the Khibiny ultramafic rocks where Cr is associated with Mg, Al (it is isomorphic with Cr), and with Ca, chromium in the fenites is associated with Fe, Ti, and V (with which Cr³⁺ is isomorphic) and with Na in silicate minerals. Cr³⁺ Mobility of Cr³⁺ and the unique character of chromium mineralization in the examined fenites were caused by high alkalinity of the fluid.     

Ab initio quantum-mechanical modeling of pyrophyllite [Al2Si4O10(OH)2] and talc [Mg3Si4O10(OH)2] surfaces

Bulk and slab geometry optimizations and calculations of the electrostatic potential at the surface of both pyrophyllite [Al₂Si₄O₁₀(OH)₂] and talc [Mg₃Si₄O₁₀(OH)₂] were performed at Hartree–Fock and DFT level. In both pyrophyllite and talc cases, a modest (001) surface relaxation was observed, and the surface preserves the structural features of the crystal: in the case of pyrophyllite the tetrahedral and octahedral sheets are strongly distorted with respect to the ideal hexagonal symmetry (and basal oxygen are located at different heights along the direction normal to the basal plane), whereas the structure of talc deviates slightly from the ideal hexagonal symmetry (almost co-planar basal oxygen). The calculated distortions are fully consistent with those experimentally observed. Although the potentials at the surface of pyrophyllite and talc are of the same order of magnitude, large topological differences were observed, which could possibly be ascribed to the differences between the surface structures of the two minerals. Negative values of the potential are located above the basal oxygen and at the center of the tetrahedral ring; above silicon the potential is always positive. The value of the potential minimum above the center of the tetrahedral ring of pyrophyllite is ?0.05 V (at 2 Å from the surface), whereas in the case of talc the minimum is ?0.01 V, at 2.7 Å. In the case of pyrophyllite the minimum of potential above the higher basal oxygen is located at 1.1 Å and it has a value of ?1.25 V, whereas above the lower oxygen the value of the potential at the minimum is ?0.2 V, at 1.25 Å; the talc exhibits a minimum of ?0.75 V at 1.2 Å, above the basal oxygen.     

High-pressure synthesis and properties of magnesiocarpholite,MgAl2[Si2O6] (OH)4

Magnesiocarpholite has been synthesized on its own composition between 15 and 25 kb water pressure and 415°–600° C. Best conditions are 25 kb-550° C, starting from a mixture of oxides and synthetic cordierite. Within the MgO-Al₂O₃-SiO₂-H₂O system, possible substitutions appear to be very limited in magnesiocarpholite. Cell-parameters are a=13.706(3), b= 20.075(3), c=5.107(l) Å, space group Ccca. The larger cell, as compared with the most magnesian natural carpholites, is tentatively ascribed to structural disorder. Preliminary stability data confirm the low-temperature character of this mineral which is shown to be a high-pressure equivalent of sudoite+quartz.     

Nepheline-bearing alkali feldspar syenite (pulaskite) in the Khibina pluton,Kola Peninsula,NW Russia: petrological investigation

The geological position and probable origin of nepheline-bearing alkaline syenite (pulaskite) found within foyaite of the Khibina pluton, Kola Peninsula, Russia, are discussed. A large body of pulaskite (4.5 km²) was identified under the Quaternary deposits in the eastern part of the pluton as a result of gravimetric surveying and drilling. Genetic relations between pulaskite and the host foyaite were examined by whole-rock chemistry, including major and trace elements, the composition of the rock-forming clinopyroxenes and the diagram of phase equilibria in the system NaAlSiO₄–KAlSiO₄–SiO₂–H₂O. The results regarding mafic silicates show that pulaskite may constitute the less evolved member of a pulaskite-foyaite series, which suggests that it was formed by feldspar fractionation from an almost eutectic phonolitic melt, the parental one for both foyaite and pulaskite. The geochemical data, however, also enable us to assume the probability of additional petrogenetic mechanisms. The trace element abundance patterns may provide preliminary evidence for a process of crustal contamination of a mantle-derived phonolite magma. This process may have contributed to the genesis of the pulaskite.     

Emplacement processes and cooling history of layered cyclic unit II-7 from the Lovozero alkaline massif (Kola Peninsula, Russia)

The Lovozero alkaline massif (Kola Peninsula, Russia) is composed of three major units. The central unit (80% of the volume) comprises numerous well developed layers composed, from bottom to roof, of an urtite–juvite–foyaite–lujavrite continuous lithological sequence (ijolite–foid-bearing alkali feldspar syenite in IUGS nomenclature). The mode of emplacement of the massif and the mechanism of formation of the layering are still under debate. Petrological, mineralogical (two stages of crystallisation) and structural evidence from the detailed analysis of one of these layers (unit II-7) is interpreted in terms of both mechanical (magmatic to sub-solidus, non-coaxial deformation) and thermal differentiation operating on a crystal-laden (alkali feldspar, high T nepheline, aegirine-augite) material of foyaitic composition. Textural and mineralogical data suggest that a sheet of foiditic magma intruded into solidified earlier units of the Lovozero layered sequence and acquired a sill-like structure on cooling.     

Perrierite-(La), (La,Ce,Ca)4(Fe2+,Mn)(Ti,Fe3+,Al)4(Si2O7)2O8, a new mineral species from the Eifel volcanic district, Germany

Non-metamict perrierite-(La) discovered in the Dellen pumice quarry, near Mendig, in the Eifel volcanic district, Rheinland-Pfalz, Germany has been approved as a new mineral species (IMA no. 2010-089). The mineral was found in the late assemblage of sanidine, phlogopite, pyrophanite, zirconolite, members of the jacobsite-magnetite series, fluorcalciopyrochlore, and zircon. Perrierite-(La) occurs as isolated prismatic crystals up to 0.5 × 1 mm in size within cavities in sanidinite. The new mineral is black with brown streak; it is brittle, with the Mohs hardness of 6 and distinct cleavage parallel to (001). The calculated density is 4.791 g/cm³. The IR spectrum does not contain absorption bands that correspond to H₂O and OH groups. Perrierite-(La) is biaxial (-), α = 1.94(1), β = 2.020(15), γ = 2.040(15), 2V _meas = 50(10)°, 2V _calc = 51°. The chemical composition (electron microprobe, average of seven point analyses, the Fe²⁺/Fe³⁺ ratio determined from the X-ray structural data, wt %) is as follows: 3.26 CaO, 22.92 La₂O₃, 19.64 Ce₂O₃, 0.83 Pr₂O₂, 2.09 Nd₂O₃, 0.25 MgO, 2.25 MnO, 3.16 FeO, 5.28 Fe₂O₃, 2.59 Al₂O₃, 16.13 TiO₂, 0.75 Nb₂O₅, and 20.06 SiO₂, total is 99.21. The empirical formula is (La_1.70Ce_1.45Nd_0.15Pr_0.06Ca_0.70)_Σ4.06(Fe _0.53 ²⁺ Mn_0.38Mg_0.08)_Σ0.99(Ti_2.44Fe _0.80 ³⁺ Al_0.62Nb_0.07)_Σ3.93Si_4.04O₂₂. The simplified formula is (La,Ce,Ca)₄(Fe²⁺,Mn)(Ti,Fe³⁺,Al)₄(Si₂O₇)₂O₈. The crystal structure was determined by a single crystal. Perrierite-(La) is monoclinic, space group P2₁/a, and the unit-cell dimensions are as follows: a =13.668(1), b = 5.6601(6), c = 11.743(1) Å, β = 113.64(1)°; V = 832.2(2) ų, Z = 2. The strong reflections in the X-ray powder diffraction pattern are [d, Å (I, %) (hkl)]: 5.19 (40) (110), 3.53 (40) ( $\overline 3 $ 11), 2.96 (100) ( $\overline 3 $ 13, 311), 2.80 (50) (020), 2.14 (50) ( $\overline 4 $ 22, $\overline 3 $ 15, 313), 1.947 (50) (024, 223), 1.657 (40) ( $\overline 4 $ 07, $\overline 4 $ 33, 331). The holotype specimen of perrierite-(La) is deposited at the Fersman Mineralogical Museum, Russian Academy of Sciences, Moscow, Russia, with the registration number 4059/1.     

The crystal structure of curite, [Pb6.56(H2O,OH)4] [(UO2)8O8(OH)6]2

Summary The crystal structure of curite, of which until now only the arrangement of the U and Pb atoms was known, has been redetermined with a synthetic crystal using three-dimensional X-ray techniques.R=0.043 for 1270 observed reflections. Curite is orthorhombic, space groupPnam-D _2h ¹⁶ ,a=12.513,b=13.002,c=8.373 ,Z=6.56 PbO·16UO₃·9.44H₂O. The structure consists of a novel type of washboard like puckered layers ² [(UO₂)₈O₈ (OH)₆]^6– formed by tetragonal bipyramidal [(UO₂)O₃(OH)] and pentagonal bipyramidal [(UO₂)O₃ (OH)₂] polyhedra. The layers are parallel to {100} and are directly connected by hydrogen bonds. Lead atoms and oxygen atoms (H₂O+OH) are located in folds between the layers, helping to connect them. The interlayer atomic positions are slightly disordered and one of them is partially occupied. The variable concentrations of the interlayer atoms are responsible for the changes in chemical composition.The structural formula [Pb_8–x (OH)_4–2x (H₂O)_2x ] [(UO₂)₈(OH)₆]₂ is suggested for curite;x=1.44 for the investigated synthetic curite. Within the three different U–O polyhedra the axial U–O distances are 1.81–1.88 , the equatorial 2.14–2.57 . The two different Pb atoms have ionic coordinations, each by ten oxygens with Pb–O distances of 2.46–3.32 , on the average 2.82 .

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Die Kristallstruktur von Curit, [Pb _6,56 (H ₂ O, OH) ₄ ] [(UO ₂)₈ O ₈(OH)₆]₂

Zusammenfassung Die Kristallstruktur von Curit, von der bisher nur die Lagen der Uran- und Bleiatome bekannt waren, wurde anhand eines künstlichen Kristalls mit dreidimensionalen Röntgendaten neu bearbeitet und für 1270 Reflexe aufR=0,043 verfeinert. Curit kristallisiert rhombisch, RaumgruppePnam-D _2h ¹⁶ ,a=12,513,b=13,002,c=8,373 ,Z=6,56 PbO·16 UO₃·9,44 H₂O. Die Struktur enthält gewellte Schichten eines neuen Typs, ² [(UO₂)₈O₈(OH)₆]^6–, die sich aus tetragonal bipyramidalen [(UO₂)O₃(OH)]- und pentagonal-bipyramidalen [(UO₂)O₃(OH)₂]-Polyedern zusammensetzen. Die Schichten verlaufen parallel {100} und sind über Wasserstoffbrücken miteinander unmittelbar verknüpft. Zwischen den Schichten befinden sich Bleiatome und zusätzliche Sauerstoffatome (H₂O+OH). Diese Atome weisen zum Teil Fehlordnung auf; eine der beiden Pb-Lagen ist nur partiell besetzt. Für Schwankungen in der chemischen Zusammensetzung von Curit ist der unterschiedliche Gehalt an Zwischenschichtatomen verantwortlich. Aufgrund dieser Untersuchung wird die Strukturformel [Pb_8–x (OH)_4–2x (H₂O)_2x ] [(UO₂)₈O₈(OH)₆]₂ vorgeschlagen; für den untersuchten Curit istx=1,44. Die drei verschiedenen U–O-Polyeder der Struktur besitzen axiale bzw. äquatoriale U–O-Abstände von 1,81–1,88 bzw. 2,14–2,57 . Die zwei Arten von Bleiatomen besitzen eine ionische Koordination; beide sind von 10 Sauerstoffatomen in Abständen von 2,46–3,32 (Mittelwert 2,82 ) umgeben.

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With 3 Figures     

A modern, guano-related occurrence of foggite, CaAl(PO4)(OH)2 · H2O and churchite-(Y), YPO4 · 2H2O in Cioclovina Cave, Romania

Summary This study reports foggite and churchite-(Y) from two spatially separate locations in the guano-related phosphate deposit from the Cioclovina Cave, Romania. Optical microscope observations, powder X-ray diffraction, electron microprobe analyses, and FTIR were used in the analysis of the two minerals. The chemical composition of foggite was determined to be Ca_0.925(Al_0.91Fe²⁺_0.016)_Σ0.926(P_0.991Si_0.043)_Σ1.034O_3.74(OH)_2.26 · H₂O and churchite-(Y) [(Y_0.830Dy_0.043Er_0.033Gd_0.029Yb_0.022)_Σ0.957Ca_0.009]P_1.023O_4.00 · 2H₂O. Chemical analyses of Cioclovina churchite-(Y) clearly revealed enrichment in lanthanides of even atomic number. The refined unit-cell parameters are for foggite (orthorhombic) a = 9.264(1) ?, b = 21.334(8) ?, c = 5.197(7) ?, and V = 1027.13(8) ?³ (Z = 8); for churchite-(Y) (monoclinic): a = 5.578(8) ?, b = 15.013(6) ?, c = 6.277(8) ?, β = 117.94(4)°, and V = 464.38(5) ?³ (Z = 4). FTIR spectrum of churchite-(Y) exhibits all the bands assigned to the vibrations of PO₄, OH, and water groups. Unlike other documented occurrences of foggite and churchite-(Y), in Cioclovina Cave, the occurrence of these minerals are related to a process that phosphatized subjacent limestone and various cave sediments (sand, clay, and limy mud) to form a complex phosphate assemblage. The minerals are presumably derived from phosphate-rich solutions that reacted with clay earth while moving downward through the sediments. Foggite was formed at the expense of the originally precipitated crandallite. Locally concentrated yttrium, REE, and dissolved phosphate are probably responsible for the precipitation of churchite-(Y). Present address: Department of Geology, University of South Florida, Tampa, FL, USA     

1Tc-Strontiohilgardit (Ca,Sr)2[B5O8(OH)2Cl] und seine Stellung in der Hilgarditgruppe X2/II[B5O8(OH)2Cl]

Zusammenfassung 1Tc-Strontiohilgardit (Ca, Sr)₂ [B₅O₈(OH)₂,Cl] mit Ca : Sr etwa 1 : 1 ist ein neues Mineral der Hilgarditgruppe. Fundpunkt: Reyersbausen (9° 59,7 E, 51° 36,6 N), Grube Königshall-Hindenburg, Flöz Staßfurt in sylvinitischer Ausbildung.Konstanten : triklin-pedial,a ₀=6,38 Å,b ₀=6,480 Å,c ₀=6,608 Å, =75,4°,=61,2°, =60,5°; tafelige-gestreckte Links- und Re chtskristalle, farblos, wasserunlöslich, piezoelektrisch. Härte 5–7, Dichte 2,99 g cm^–3;n =1,638,n =1,639,n =1,670; 2V =19°.Neue Daten für die Hilgarditgruppe : 2 M (Cc)-Calciumhilgardit (=Hilgardit) =4 Ca₂[B₅O₃(OH)₂Cl], Raumgruppe Cc.3Tc-Calciumhilgardit (=Parahilgardit) = 3 Ca₂[B₅O₃(OH)₂Cl]; trinklin-pedial, ₀=6,31 Å,b =6,484 Å,c ₀=17,50 Å; =84,0°,=79,6°, =60,9°.Die Polymorphiebeziehungen sind geometrisch deutbar durch eine spezielle Art der Polytropie (Stapelung von Links- und Rechtskristallen im Elementarbereich).     

Batisite,Na2BaTi2(Si4O12)O2, from Inagli massif,Aldan, Russia: crystal-structure refinement and high-temperature X-ray diffraction study

Mineralogy and Petrology - The crystal structure of batisite, Na2BaTi2 (Si4O12)O2, from the Inagli massif (Aldan, Yakutia, Russia) was refined to R 1 = 0.032 for 1449 unique...     

Karchevskyite, [Mg18Al9(OH)54][Sr2(CO3,PO4)9(H2O,H3O)11], a new mineral species of the layered double hydroxide family

Karchevskyite, a new mineral related to the family of layered double hydroxides (LDHs), has been found in the Iron open pit at the Kovdor carbonatite massif, Kola Peninsula, Russia. The mineral occurs as spherulites of up to 1.5 mm in diameter composed of thin, curved lamellae. Dolomite, magnetite, quintinite-3T, strontium carbonate, and fluorapatite are associated minerals. Karchevskyite is white in aggregates and colorless in separate platelets. Its luster is vitreous with a pearly shine on the cleavage surface. The new mineral is nonfluorescent. The Mohs hardness is 2. The cleavage is eminent (micalike), parallel to {001}. The measured density is 2.21(2) g/cm³, and the calculated value is 2.18(1) g/cm³. Karchevskyite is colorless and nonpleochroic in immersion liquids. It is uniaxial, negative, ω = 1.542(2), and ? = 1.534(2). The chemical composition (electron microprobe, average of ten point analyses, standard deviation in parentheses, wt %) is as follows: 29.7(1.1) MgO, 18.3(0.7) Al₂O₃, 7.4(0.4) SrO, 0.2(0.1) CaO, 1.3(0.2) P₂O₅, 14.5(0.4) CO₂, and 28.6 H₂O (estimated by difference); the total is 100. The empirical formula calculated on the basis of nine Al atoms is Mg_18.00Al_9.00(OH)_54.00(Sr_1.79Mg_0.48Ca_0.09)_2.36 (Ca₃)_8.26(PO₄)_0.46(H₂O)_6.54(H₃O)_4.18. The idealized formula is [Mg₁₈Al₉(OH)₅₄][Sr₂(CO₃, PO₄)₉(H₂O, H₃O)₁₁]. The new mineral slowly dissolves in 10% HCl with weak effervescence. Karchevskyite is trigonal; possible space groups are P3, P3, P $ \overline 3 Karchevskyite, a new mineral related to the family of layered double hydroxides (LDHs), has been found in the Iron open pit at the Kovdor carbonatite massif, Kola Peninsula, Russia. The mineral occurs as spherulites of up to 1.5 mm in diameter composed of thin, curved lamellae. Dolomite, magnetite, quintinite-3T, strontium carbonate, and fluorapatite are associated minerals. Karchevskyite is white in aggregates and colorless in separate platelets. Its luster is vitreous with a pearly shine on the cleavage surface. The new mineral is nonfluorescent. The Mohs hardness is 2. The cleavage is eminent (micalike), parallel to {001}. The measured density is 2.21(2) g/cm³, and the calculated value is 2.18(1) g/cm³. Karchevskyite is colorless and nonpleochroic in immersion liquids. It is uniaxial, negative, ω = 1.542(2), and ɛ = 1.534(2). The chemical composition (electron microprobe, average of ten point analyses, standard deviation in parentheses, wt %) is as follows: 29.7(1.1) MgO, 18.3(0.7) Al₂O₃, 7.4(0.4) SrO, 0.2(0.1) CaO, 1.3(0.2) P₂O₅, 14.5(0.4) CO₂, and 28.6 H₂O (estimated by difference); the total is 100. The empirical formula calculated on the basis of nine Al atoms is Mg_18.00Al_9.00(OH)_54.00(Sr_1.79Mg_0.48Ca_0.09)_2.36 (Ca₃)_8.26(PO₄)_0.46(H₂O)_6.54(H₃O)_4.18. The idealized formula is [Mg₁₈Al₉(OH)₅₄][Sr₂(CO₃, PO₄)₉(H₂O, H₃O)₁₁]. The new mineral slowly dissolves in 10% HCl with weak effervescence. Karchevskyite is trigonal; possible space groups are P3, P3, P 1m, P31m, P312, P312, P3m1, or P3m1; unit-cell dimensions are a = 16.055(6), c = 25.66(1) ?, V = 5728(7) ?³, Z = 3. The strongest reflections in the X-ray powder diffraction pattern [d, (I, %)(hkl)] are: 8.52(10)(003), 6.41(4)(004), 5.13(3)(005), 4.27(6)(006), 3.665(9)(007), 3.547(9)(107), 3.081(6)(315). Wavenumbers of absorption bands in the infrared spectrum of the new mineral are (cm⁻¹; s is shoulder): 3470, 3420s, 3035, 2960s, 1650, 1426, 1366, 1024, 937, 860, 779, 678, 615s, 553, 449, 386. Results of thermogravimetric analysis: total weight loss is 42.0 wt %, with three stages of loss: 12.2%, maximum rate at 230°C; 6.1%, maximum rate at 320°C; and 23.7%, maximum rate at 440°C. Karchevskyite is a late-stage hydrothermal mineral. The mineral is named in memory of Russian mineralogist Pavel Karchevsky (1976–2002), who made a significant contribution to the study of carbonatites. The type material of karchevskyite is deposited at the Mineralogical Museum, Division of Mineralogy, St. Petersburg State University, and the Fersman Mineralogical Museum, Russian Academy of Sciences, Moscow. Original Russian Text ? S.N. Britvin, N.V. Chukanov, G.K. Bekenova, M.A. Yagovkina, A.V. Antonov, A.N. Bogdanova, N.I. Krasnova, 2007, published in Zapiski Rossiiskogo Mineralogicheskogo Obshchestva, 2007, No. 5, pp. 44–56. The new mineral karchevskyite and its name accepted by the Commission on New Minerals and Mineral Names, Russian Mineralogical Society, March 21, 2005. Approved by the Commission on New Minerals and Mineral Names, International Mineralogical Association, June 30, 2005.     

Chemistry, Raman and infrared spectroscopic characterization of the phosphate mineral reddingite: (MnFe)3(PO4)2(H2O,OH)3, a mineral found in lithium-bearing pegmatite

Detailed investigation of an intermediate member of the reddingite–phosphoferrite series, using infrared and Raman spectroscopy, scanning electron microcopy and electron microprobe analysis, has been carried out on a homogeneous sample from a lithium-bearing pegmatite named Cigana mine, near Conselheiro Pena, Minas Gerais, Brazil. The determined formula is $ ({\text{Mn}}_{1.60} {\text{Fe}}_{1.21} {\text{Ca}}_{0.01} {\text{Mg}}_{0.01} )_{\sum 2.83} ({\text{PO}}_{4} )_{2.12} \cdot ({\text{H}}_{2} {\text{O}}_{2.85} {\text{F}}_{0.01} )_{\sum 2.86} $ , indicating predominance in the reddingite member. Raman spectroscopy coupled with infrared spectroscopy supports the concept of phosphate, hydrogen phosphate and dihydrogen phosphate units in the structure of reddingite-phosphoferrite. Infrared and Raman bands attributed to water and hydroxyl stretching modes are identified. Vibrational spectroscopy adds useful information to the molecular structure of reddingite–phosphoferrite.     

Synthesis and physical properties of piemontite Ca2Al3-pMn p 3+ (Si2O7/SiO4/O/OH)

Mn³⁺-bearing piemontites and orthozoisites, Ca₂(Al_3-pMn³⁺ _p)-(Si₂O₇/SiO₄/O/OH), have been synthesized on the join Cz (p = 0.0)-Pm (p = 3.0) of the system CaO-Al₂O₃-(MnO·MnO₂)-SiO₂-H₂O atP = 15 kb,T= 800 °C, and \(f_{O_2 } \) of the Mn₂O₃/MnO₂ buffer. Pure Al-Mn³⁺-piemontites were obtained with 0.5≦p≦1.75, whereas atp=0.25 Mn³⁺-bearing orthozoisite (thulite) formed as single phase product. The limit of piemontite solid solubility is found near p=1.9 at the above conditions. Withp>1.9, the maximum piemontite coexisted with a new high pressure phase CMS-X1, a Ca-bearing braunite (Mn _0.2 ²⁺ Ca_0.8)Mn ₆ ³⁺ O₈(SiO₄), and quartz. Al-Mn³⁺-piemontite lattice constants (LC),b ₀,c ₀,V ₀, increase with increasingp:

Tveitite-(Y) and REE-enriched fluorite from amazonite pegmatites of the Western Keivy,Kola Peninsula,Russia: Genetic crystal chemistry of natural Ca,REE-fluorides

Tveitite-(Y) as pods up to 10 cm across has been found at Mt. Rovgora, the Western Keivy, Kola Peninsula, Russia, in an albite-quartz-amazonite pegmatite vein related to alkaline granite. Tveitite-(Y) grains (up to 4 cm) are parallel microintergrowths of two isostructural varieties, Ca_9.5Na_1.7Y_5.2Ln_2.0F_42.6 and Ca_11.4Na_1.9Y_4.4Ln_1.4F_42.0. The idealized structural formula (Z = 3) is (Y, Na)₆(Ca, LREE)₆(Ca, Na, HREE)₆(Ca, Na)F₄₂; the simplified formula is (Ca, REE, Na)₁₃(Y, Na)₆F₄₂; space group R \(\bar 3\) a = 17.020, c = 9.679 Å. [Lanthanoides are abbreviated in this paper as Ln, whereas Ln + Y as REE]. Nine fluorite samples containing from 0 to 18 mol % (REE)F₃ were examined by electron microprobe, X-ray powder diffraction, and IR spectroscopy. The crystal structure of natural yttrofluorite has been determined for the first time (R _aniso = 1.47 %): Fm3m, a = 5.493 Å; the structural formula is (Ca_0.82Y_0.12Ln_0.06)F_2.15. Earlier published and new data show that yttrofluorite containing (REE)F₃ > 20 mol % and REE-enriched fluorite with LREE > Y (HREE) are metastable under room conditions. In nature, tveitite-(Y) is a product of solid-state transformation of metastable yttrofluorite with (REE)F₃ > 20 mol %. Inferred protophases could have been exsolved into tveitite-(Y) variable in composition or tveitite-(Y) + yttrofluorite stable under normal conditions. The formation of tveitite-(Y) requires the erichment of a protophase not only in Y but also in LREE and HREE as stabilizing admixtures regularly distributed by different types of Ca-dominant structural sites. Tveitite-(Y) and yttrofluorite are geochemical indicators of a medium that is not only enriched in Y, Ln, and F, but also depleted in Na, Ca, CO₂ and P.