Calcium-aluminum-silicate-hydrate "cement" phases and rare Ca-zeolite association at Colle Fabbri, Central Italy

Abstract Very high temperature, Ca-rich alkaline magma intruded an argillite formation at Colle Fabbri, Central Italy, producing cordierite-tridymite metamorphism in the country rocks. An intense Ba-rich sulphate-carbonate-alkaline hydrothermal plume produced a zone of mineralization several meters thick around the igneous body. Reaction of hydrothermal fluids with country rocks formed calcium-silicate-hydrate (CSH), i.e., tobermorite-afwillite-jennite; calcium-aluminum-silicate-hydrate (CASH) — "cement" phases - i.e., thaumasite, strätlingite and an ettringite-like phase and several different species of zeolites: chabazite-Ca, willhendersonite, gismon-dine, three phases bearing Ca with the same or perhaps lower symmetry of phillipsite-Ca, levyne-Ca and the Ca-rich analogue of merlinoite. In addition, apophyllite-(KF) and/or apophyllite-(KOH), Ca−Ba-carbonates, portlandite and sulphates were present. A new polymorph from the pyrrhotite group, containing three layers of sphalerite-type structure in the unit cell, is reported for the first time. Such a complex association is unique. Most of these minerals are specifically related to hydration processes of: (1) pyrometamorphic metacarbonate/metapelitic rocks (natural analogues of cement clinkers); (2) mineralization between intrusive stocks and slates; and (3) high-calcium, alkaline igneous rocks such as melilitites and foidites as well as carbonatites. The Colle Fabbri outcrop offers an opportunity to study in situ complex crystalline overgrowth and specific crystal chemistry in mineral phases formed in igneous to hydrothermal conditions

Copper-Containing Magnesioferrite in Vesicular Trachyandesite in a Lava Tube from the 2012-2013 Eruption of the Tolbachik Volcano, Kamchatka, Russia

Cu-rich magnesioferrite was found in vesicular basaltic trachyandesite in one of lava tubes (Duplex) that formed during the 2012-2013 eruption of the Tolbachik volcano, Kamchatka. This mineral is commonly associated with hematite, tenorite, halite, sylvite, and Ca-rich silicates (mainly, esseneite and Na-rich melilite) in high-temperature (800-1000 degrees C) reactionary zones (up to 100 mu m) covering vesicular rocks and lava stalactites in the Duplex tube. The mineral relationships of this assemblage indicate the following crystallization sequence: Ca-rich silicates + hematite -> Cu-rich magnesioferrite -> tenorite -> chlorides. This formed due to the reaction of hot gases containing Cu, alkalis, and Cl with solidified lava rock. The composition of magnesioferrite varies strongly in CuO (5.8-17.3 wt %; cuprospinel end-member-15-47 mol %), whereas the contents of other oxides are minor, indicating the main isomorphic substitution is Mg2+ Cu2+. Compositions with maximal CuO content nominally belong to Mg-rich cuprospinel: (Cu0.48Mg0.41Mn0.09Zn0.02Ca0.02) (Fe1.943+Al0.03Ti0.02)O-4. Increasing CuO content of the Duplex Cu-rich magnesioferrite is reflected in Raman spectra by moderate right shifting bands at approximate to 700-710 and 200-210 cm(-1) and the appearance of an additional band at 596 cm(-1). This supports the main isomorphic scheme and may indicate a degree of inversion in the spinel structure.Peer reviewe

Nataliakulikite, Ca4Ti2(Fe3+,Fe2+)(Si,Fe3+,Al)O11, a New Perovskite-Supergroup Mineral from Hatrurim Basin, Negev Desert, Israel

Nataliakulikite, Ca4Ti2(Fe3+,Fe2+)(Si,Fe3+,Al)O11, is a mineral intermediate between perovskite CaTiO3 and brownmillerite Ca2(Fe,Al)2O5. It was discovered as a minor mineral in a high-temperature pyrometamorphic larnite-gehlenite rock at the Nahal Morag Canyon of the Hatrurim Basin, Israel. Nataliakulikite is associated with larnite, flamite, gehlenite, magnesioferrite, Fe3+-rich perovskite, fluorapatite, barite, Hashemite, and retrograde phases (afwillite, hillebrandite, portlandite, calcite, ettringite, hydrogarnet, and other hydrated Ca-silicates). The mineral forms brown subhedral or prismatic grains (up to 20 µm) and their intergrowths (up to 50 μm). Its empirical formula (n = 47) is (Ca3.992Sr0.014U0.004)(Ti1.933Zr0.030Nb0.002) (Fe3+0.610Fe2+0.405Cr0.005Mn0.005)(Si0.447Fe3+0.337Al0.216)O11 and shows Si predominance in tetrahedral site. The unit-cell parameters (HRTEM data) and space group are: a = 5.254, b = 30.302, c = 5.488 Å, V = 873.7 Å3, Pnma, Z = 4. These dimensions and Electron backscatter diffraction (EBSD) data strongly support the structural identity between nataliakulikite and synthetic Ca4Ti2Fe3+2O11 (2CaTiO3∙Ca2Fe3+2O5), an intermediate compound in the system CaTiO3-Ca2Fe3+2O5. In general, this mineral is a Si-Fe2+-rich natural analog of synthetic Ca4Ti2Fe3+2O11. The X-ray powder diffraction data (CuKα -radiation), calculated from unit-cell dimensions, show the strongest lines {d [Å], (Icalc)} at: 2.681(100), 1.898(30), 2.627(26), 2.744(23), 1.894(22), 15.151(19), 1.572(14), 3.795(8). The calculated density is 4.006 g/cm3. The crystal structure of nataliakulikite has not been refined because of small sizes of grains. The Raman spectrum shows strong bands at 128, 223, 274, 562, and 790 cm−1. Nataliakulikite from the Hatrurim Basin crystallized under the conditions of combustion metamorphism at high temperatures (1160–1200 °C) and low pressures (HT-region of the spurrite-merwinite facies)

Rippite, K2(Nb,Ti)2(Si4O12)O(O,F), a New K-Nb-Cyclosilicate from Chuktukon Carbonatite Massif, Chadobets Upland, Krasnoyarsk Territory, Russia

Rippite K2(Nb,Ti)2(Si4O12)(O,F)2, a new K-Nb-cyclosilicate, has been discovered in calciocarbonatites from the Chuktukon massif (Chadobets upland, SW Siberian Platform, Krasnoyarsk Territory, Russia). It was found in a primary mineral assemblage, which also includes calcite, fluorcalciopyrochlore, tainiolite, fluorapatite, fluorite, Nb-rich rutile, olekminskite, K-feldspar, Fe-Mn–dolomite and quartz. Goethite, francolite (Sr-rich carbonate–fluorapatite) and psilomelane (romanèchite ± hollandite) aggregates as well as barite, monazite-(Ce), parisite-(Ce), synchysite-(Ce) and Sr-Ba-Pb-rich keno-/hydropyrochlore are related to a stage of metasomatic (hydrothermal) alteration of carbonatites. The calcite–dolomite coexistence assumes crystallization temperature near 837 °C for the primary carbonatite paragenesis. Rippite is tetragonal: P4bm, a = 8.73885(16), c = 8.1277(2) Å, V = 620.69(2) Å3, Z = 2. It is closely identical in the structure and cell parameters to synthetic K2Nb2(Si4O12)O2 (or KNbSi2O7). Similar to synthetic phase, the mineral has nonlinear properties. Some optical and physical properties for rippite are: colorless; Mohs’ hardness—4–5; cleavage—(001) very perfect, (100) perfect to distinct; density (meas.)—3.17(2) g/cm3; density (calc.)—3.198 g/cm3; optically uniaxial (+); ω = 1.737-1.739; ε = 1.747 (589 nm). The empirical formula of the holotype rippite (mean of 120 analyses) is K2(Nb1.90Ti0.09Zr0.01)[Si4O12](O1.78OH0.12F0.10). Majority of rippite prismatic crystals are weakly zoned and show Ti-poor composition K2(Nb1.93Ti0.05Zr0.02)[Si4O12](O1.93F0.07). Raman and IR spectroscopy, and SIMS data indicate very low H2O content (0.09–0.23 wt %). Some grains may contain an outermost zone, which is enriched in Ti (+Zr) and F, up to K2(Nb1.67Ti0.32Zr0.01)[Si4O12](O1.67F0.33). It strongly suggests the incorporation of (Ti,Zr) and F in the structure of rippite via the isomorphism Nb5+ + O2− → (Ti,Zr)4+ + F1−. The content of a hypothetical end-member K2Ti2[Si4O12]F2 may be up to 17 mol. %. Rippite represents a new structural type among [Si4O12]-cyclosilicates because of specific type of connection of the octahedral chains and [Si4O12]8− rings. In structural and chemical aspects it seems to be in close with the labuntsovite-supergroup minerals, namely with vuoriyarvite-(K), K2(Nb,Ti)2(Si4O12)(O,OH)2∙4H2O

Petrology of alkaline silicate rocks and carbonatites of the Chuktukon massif, Chadobets upland, Russia: Sources, evolution and relation to the Triassic Siberian LIP

The petrogenesis of temporally and spatially associated carbonatitic and deeply derived carbonated alkaline silicate magmas provides an opportunity to gain insights into the nature of the deepest lithospheric mantle. The Chuktukon massif, which is part of the Chadobets alkaline ultramafic carbonatite complex (Chadobets upland, Siberian craton) is a carbonatite-melilitite-damtjernite intrusion, whose emplacement was coeval with the Siberian Traps large igneous province (LIP). In this study, the sources of the primary melts are examined, the petrogenetic evolution of the complex is reconstructed and the relationship with the Siberian LIP is also discussed. Isotopic and geochemical information indicate that the source for the Chuktukon primary melts was isotopically moderately depleted and the primary melts were formed by low degree partial melting of garnet carbonated peridotite. Hydrothermal processes caused 18O- and 13C- enrichment. The weathering process was accompanied by trace element re-distribution and enrichment of the weathering crust in Zn, Th, U, Nb, Pb and REE, relative to the Chuktukon rocks and a change in radiogenic (Sr, Nd) isotope compositions