G. Yu. Ivanyuk

Crystal chemistry of natural layered double hydroxides. I. Quintinite-2H-3c from the Kovdor alkaline massif, Kola peninsula, Russia

Abstract The crystal structure of quintinite-2H-3c, [Mg4Al2(OH)12](CO3)(H2O)3, from the Kovdor alkaline massif, Kola peninsula, Russia, was solved by direct methods and refined to an agreement index (R1) of 0.055 for 484 unique reflections with |Fo| ≥ 4σF. The mineral is rhombohedral, R32, a = 5.2745(7), c = 45.36(1) Å. The diffraction pattern of the crystal has strong and sharp Bragg reflections having h-k = 3n and l = 3n and lines of weak superstructure reflections extended parallel to c* and centred at h-k ≠ 3n. The structure contains six layers within the unit cell with the layer stacking sequence of ...AC=CA=AC=CA=AC=CA... The Mg and Al atoms are ordered in metal hydroxide layers to form a honeycomb superstructure. The full superstructure is formed by the combination of two-layer stacking sequence and Mg-Al ordering. This is the first time that a long-range superstructure in carbonate-bearing layered double hydroxide (LDH) has been observed. Taking into account Mg-Al ordering, the unique layer sequence can be written as ...=Ab1C=Cb1A=Ab2C=Cb2A=Ab3C=Cb3A=... The use of an additional suffix is proposed in order to distinguish between LDH polytypes having the same general stacking sequence but with different c parameters compared with the ‘standard’ polytype. According to this notation, the quintinite studied here can be described as quintinite-2H-3c or quintinite-2H-3c[6R], indicating the real symmetry.

Crystal chemistry of natural layered double hydroxides. 2. Quintinite-1M: first evidence of a monoclinic polytype in M2+-M3+ layered double hydroxides

Abstract Quintinite-1M, [Mg4Al2(OH)12](CO3)(H2O)3, is the first monoclinic representative of both synthetic and natural layered double hydroxides (LDHs) based on octahedrally coordinated di- and trivalent metal cations. It occurs in hydrothermal veins in the Kovdor alkaline massif, Kola peninsula, Russia. The structure was solved by direct methods and refined to R1 = 0.031 on the basis of 304 unique reflections. It is monoclinic, space group C2/m, a = 5.266(2), b = 9.114(2), c = 7.766(3) Å, β = 103.17(3)º, V = 362.9(2) Å3. The diffraction pattern of quintinite-1M contains sharp reflections corresponding to the layer stacking sequence characteristic of the 3R rhombohedral polytype, and rows of weak superlattice reflections superimposed upon a background of streaks of modulated diffuse intensity parallel to c*. These superlattice reflections indicate the formation of a 2-D superstructure due to Mg-Al ordering. The structure consists of ordered metal hydroxide layers and a disordered interlayer. As the unit cell contains exactly one layer, the polytype nomenclature dictates that the mineral be called quintinite-1M. The complete layer stacking sequence can be described as ...=Ac1B=Ba1C=Cb1A=... Quintinite-1M is isostructural with the monoclinic polytype of [Li2Al4(OH)12](CO3)(H2O)3.

Crystal chemistry of natural layered double hydroxides. 3. The crystal structure of Mg,Al-disordered quintinite-2H

Abstract Two crystals of Mg, Al-disordered quintinite-2H (Q1 and Q2), [Mg4Al2(OH)12](CO3)(H2O)3, from the Kovdor alkaline massif, Kola peninsula, Russia, have been characterized chemically and structurally. Both crystals have hexagonal symmetry, P63/mcm, a = 3.0455(10)/3.0446(9), c = 15.125(7)/15.178(5) Å, V = 121.49(8)/121.84(6) Å3. The structures of the two crystals have been solved by direct methods and refined to R1 = 0.046 and 0.035 on the basis of 76 and 82 unique observed reflections for Q1 and Q2, respectively. Diffraction patterns obtained using an image-plate area detector showed the almost complete absence of superstructure reflections which would be indicative of the Mg-Al ordering in metal hydroxide layers, as has been observed recently for other quintinite polytypes. The crystal structures are based on double hydroxide layers [M(OH)2] with an average disordered distribution of Mg2+ and Al3+ cations. Average bond lengths for the metal site are 2.017 and 2.020 Å for Q1 and Q2, respectively, and are consistent with a highly Mg-Al disordered, average occupancy. The layer stacking sequence can be expressed as ...=AC=CA=..., corresponding to a Mg-Al-disordered 2H polytype of quintinite. The observed disorder is probably the result of a relatively high temperature of formation for the Q1 and Q2 crystals compared to ordered polytypes. This suggestion is in general agreement with the previous observations which demonstrated, for the Mg-Al system, a higher-temperature regime of formation of the hexagonal (or pseudo-hexagonal in the case of quintinite-2H-3c) 2H polytype in comparison to the rhombohedral (or pseudo-rhombohedral in the case of quintinite-1M) 3R polytype.

Trap formation of the Kola peninsula

The nepheline syenites and foidolites of the world’s largest Lovozero and Khibiny allkaline massifs contain numerous xenoliths of intercalating olivine basalts, their tuffs, tuffites, and quartzitosandstones that experienced more (in the Khibiny Massif) or less (in the Lovozero Massif) intense thermal-metasomatic transformation. In terms of geological, petrographical, and petrochemical features, the unaltered rocks of the Lovozero Formation can be ascribed to the rocks of the trap formation, while all wealth of the rocks formed during their contact-metasomatic alteration (sekaninaite-anorthoclase, annite-anorthoclase, fayalite-anorthoclase, rutile-freudenbergite-anorthoclase, topaz-andalusite-anorthoclase, and others) was formed due to alkaline metasomatism. The Fourier analysis of the color variation curves for the volcanogenic-sedimentary rocks revealed the identity between bedding of initial tuffs (tuffites) and banding of their fenitized analogues.

Whiteite-(CaMnMn), CaMnMn2Al2[PO4]4(OH)2·8H2O, a new mineral from the Hagendorf-Süd granitic pegmatite, Germany

Abstract Whiteite-(CaMnMn), CaMnMn2Al2[PO4]4(OH)2·8H2O, is a new hydrous phosphate of Ca, Mn and Al, which is closely related to both jahnsite-(CaMnMn) and the minerals of the whiteite group. It is monoclinic, P2/a, with a = 15.02(2), b = 6.95(1), c =10.13(3) Å, β = 111.6(1)º, V = 983.3(6) Å3, Z = 2 (from powder diffraction data) or a = 15.020(5), b = 6.959(2), c = 10.237(3) Å, β = 111.740(4)º, V = 984.3(5) Å3, Z = 2 (from single-crystal diffraction data). The mineral was found in the Hagendorf Süd granitic pegmatite (Germany) as small (up to 0.5 mm in size) crystals elongated on a and tabular on {010}. The crystals are either simply or polysynthetically twinned on {001}. They crystallize on the walls of voids within altered zwieselite crystals or form coronas (up to 1 mm in diameter) around cubic crystals of uraninite. The mineral is transparent, colourless to pale yellow (depending on Al-Fe3+ substitution), with a vitreous lustre and a white streak. The cleavage is perfect on {001}, the fracture is stepped and the Mohs hardness is 3½. In transmitted light, the mineral is colourless; dispersion was not observed. Whiteite-(CaMnMn) is biaxial (+), α = 1.589(2), β = 1.592(2), γ = 1.601(2) (589 nm), 2Vmeas = 60(10)º, 2Vcalc = 60.3º. The optical orientation is X = b, Z^a = 5º. The calculated and measured densities are Dcalc = 2.768 and Dmeas = 2.70(3) g cm-3, respectively. The mean chemical composition determined by electron microprobe is Na2O 0.53, MgO 0.88, Al2O3 11.66, P2O5 34.58, CaO 4.29, MnO 17.32, FeO 8.32, ZnO 2.60 wt.%, with H2O 19.50 wt.% (determined by the Penfield method), giving a total of 99.68 wt.%. The empirical formula calculated on the basis of four phosphorus atoms per formula unit, with ferric iron calculated to maintain charge balance, is (Ca0.63Zn0.26Na0.14)∑1.03(Mn0.60Fe0.402+)∑1.00(Mn1.40Fe0.372+Mg0.18Fe0.063+)∑2.01(Al1.88Fe0.123+)∑2.00[PO4]4(OH)2·7.89H2O. The simplified formula is CaMnMn2Al2[PO4]4(OH)2·8H2O. The mineral is easily soluble in 10% HCl at room temperature. The strongest X-ray powder-diffraction lines [listed as d in Å (I) (hkl)] are as follows: 9.443(65)(001), 5.596(25)(011), 4.929(80)(210), 4.719(47)(002), 3.494(46)(400), 2.7958(100)(022). The crystal structure of whiteite-(CaMnMn) was refined for a single crystal twinned on (001) to R1 = 0.068 on the basis of 5702 unique observed reflections. It is similar to the structures of other members of the whiteite group. The mineral is named for the chemical composition, in accordance with whiteitegroup nomenclature.

Amphiboles of the Khibiny alkaline pluton, Kola Peninsula, Russia

The rocks of the Khibiny pluton contain 25 amphibole varieties, including edenite, fluoredenite, kaersutite, pargasite, ferropargasite, hastingsite, magnesiohastingsite, katophorite, ferrikatophorite, magnesiokatophorite, magnesioferrikatophorite, magnesioferrifluorkatophorite, ferrimagnesiotaramite, ferrorichterite, potassium ferrorichterite, richterite, potassium richterite, potassium fluorrichterite, arfvedsonite, potassium arfvedsonite, magnesioarfvedsonite, magnesioriebeckite, ferriferronyboite, ferrinyboite, and ferroeckermannite. The composition of rock-forming amphiboles changes symmetrically relative to the Central Ring of the pluton; i.e., amphiboles enriched in K, Ca, Mg, and Si are typical of foyaite near and within the Central Ring. The Fe and Mn contents in amphiboles increase in the direction from marginal part of the pluton to its center. Foyaite of the marginal zone contains ferroeckermannite, richterite, arfvedsonite, and ferrorichterite; edenite is typical of foyaite and hornfels of the Minor Arc. Between the Minor Arc and the Central Ring, foyaite contains ferroeckermannite, arfvedsonite, and richterite; amphiboles in rischorrite, foidolite and hornfels of the Central Ring are (potassium) arfvedsonite, (potassium) richterite, magnesiokatophorite, magnesioarfvedsonite, ferroeckermannite, and ferriferronyboite; amphiboles in foyaite within the Central Ring, in the central part of the pluton, are arfvedsonite, magnesioarfvedsonite, ferriferronyboite, katophorite, and richterite. It is suggested that such zoning formed due to the alteration of foyaite by a foidolite melt intruded into the Main (Central) Ring Fault.

FRACTAL ANALYSIS OF SEISMIC AND GEOLOGICAL DATA

Abstract Continental lithosphere is a highly organised physical medium which can be investigated by seismic methods to obtain objective information. The use of fractal representation offers new possibilities to determine quantitative parameters of the structural arrangement of the lithosphere and to compare tectonic structures composed of a similar set of “participants” i.e. structural complexes with a relatively homogeneous range of rocks. Fractals as a universal property of continental crust are shown to be an important tool for a comparative study of geological and seismic sections on a quantitative basis, and also in reassessing many of the previous interpretations of seismic and geological structures.

Pyroxenes of the Khibiny alkaline pluton, Kola Peninsula

Seven pyroxene varieties were identified in nepheline syenites and foidolites of the Khibiny pluton: enstatite, ferrosilite, diopside, hedenbergite, augite, aegirine-augite, and aegirine. Enstatite and augite are typical of alkaline and ultramafic rocks of dike series. Ferrosilite was found in country quartzitic hornfels. Diopside is a rock-forming mineral in alkaline and ultramafic rocks, alkali gabbroids, hornfels in xenoliths of volcanic and sedimentary rocks and foyaite, melteigite-urtite that assimilate them, and certain hydrothermal pegmatite veins. Hedenbergite was noted in hornfels from xenoliths of volcanic and sedimentary rocks and in a hydrothermal pegmatite vein at Mount Eveslogchorr. Aegirine-augite is the predominant pyroxene in all types of nepheline syenites, phonolites and tinguaites, foidolites, alkaline and ultramafic rocks of dike series, fenitized wall rocks surrounding the pluton, and xenoliths of Devonian volcanic and sedimentary rocks. Aegirine is an abundant primary or, more often, secondary mineral in nepheline syenites, foidolites, and hydrothermal pegmatite veins. It occurs as separate crystals, outer zones of diopside and aegirine-augite crystals, and homoaxial pseudomorphs after Na-Ca amphiboles. Microprobe analyses of 265 pyroxenes samples allowed us to distinguish ten principal trends of isomorphic replacement and corresponding typomorphic features of pyroxenes. Compositional variations in clinopyroxenes along the sampled 35-km profile from the margin of the Khibiny pluton to its center confirm the symmetric zoning of the foyaite pluton relative to semicircular faults of the Minor Arc and the Main (Central) Ring marked by Devonian volcanic and sedimentary rocks, foidolites, and related metasomatic rocks (rischorrite, albitite, and aegirinite). Changes in the composition of pyroxenes are explained mainly by the redistribution of elements between coexisting minerals of foyaites in the process of their intense differentiation under the effect of foidolite melts that have intruded into the circular fault zones.

Corundum-group minerals in rocks of the Khibiny alkaline pluton, Kola Peninsula

Five minerals of the corundum group have been identified in the Khibiny pluton with certainty. Corundum proper and karelianite occur only in hornfels after volcanic and sedimentary rocks. Xenoliths of hornfels mark the ring faults that bound foidalite within the field of foyaite. Hematite occurs in hydrothermally altered nepheline syenite and crosscutting hydrothermal veins related to the ring faults. Minerals of the ilmenite-pyrophanite series are present in all rocks of the pluton, including veins. Accessory ilmenite in foyaite varies from the manganese variety and pyrophanite in the inner and outer parts of the pluton to manganese-free ilmenite in zone of the Main Ring Fault. In xenoliths of volcanic rocks and alkaline ultramafic rocks, ilmenite is enriched in magnesium. The zoning in distribution of the above-mentioned minerals and the character of variation in their compositions from margins of the pluton to its center are consistent with the petrochemical zoning formed as a result of foyaite alteration of near ring faults.

Rock-Forming feldspars of the Khibiny alkaline pluton, Kola Peninsula, Russia

This paper describes the structural-compositional zoning of the well-known Khibiny pluton in regard to rock-forming feldspars. The content of K-Na-feldspars increases inward and outward from the Main foidolite ring. The degree of coorientation of tabular K-Na-feldspar crystals sharply increases in the Main ring zone, and microcline-dominant foyaite turns into orthoclase-dominant foyaite. The composition of K-Na-feldspars in the center of the pluton and the Main ring zone is characterized by an enrichment in Al. This shift is compensated by a substitution of some K and Na with Ba (the Main ring zone) or by an addition of K and Na cations to the initially cation-deficient microcline (the central part of the pluton). Feldspars of volcanosedimentary rocks occurring as xenoliths in foyaite primarily corresponded to plagioclase An15–40, but high-temperature fenitization and formation of hornfels in the Main ring zone gave rise to the crystallization of anorthoclase subsequently transformed into orthoclase and albite due to cooling and further fenitization. Such a zoning is the result of filling the Main ring fault zone within the homogeneous foyaite pluton with a foidolite melt, which provided the heating and potassium metasomatism of foyaite and xenoliths of volcanosedimentary rocks therein. The process eventually led to the transformation of foyaite into rischorrite-lyavochorrite, while xenoliths were transformed into aluminum hornfels with anorthoclase, annite, andalusite, topaz, and sekaninaite.