Heyerdahlite, Na₃Mn₇Ti₂(Si₄O₁₂)₂O₂(OH)₄F(H₂O)₂, a new mineral of the astrophyllite supergroup from the Larvik Plutonic complex, Norway: Description and crystal structure

Abstract

Heyerdahlite, ideally Na3Mn7Ti2(Si4O12)2O2(OH)4F(H2O)2, is a new astrophyllite-supergroup mineral from the Larvik Plutonic complex, Norway. Heyerdahlite was found in a nepheline-syenite pegmatite with albite, aegirine, hastingsite/magnesio-hastingsite, kupletskite, lorenzenite and pyrophanite. Heyerdahlite is colourless to pale brown, transparent and has a vitreous lustre. Mohs hardness is 3, Dcalc. = 3.245 g/cm3. Heyerdahlite is biaxial (+), α = 1.694(2), β = 1.710(5), γ = 1.730(5), 2Vmeas. = 80(4)° and 2Vcalc. = 84.5°. Cleavage is perfect parallel to {001}. The empirical formula based on 32.18 (O + F) apfu is (Na1.18K0.68Rb0.12Cs0.01Pb0.01)Σ2Na1.00(Mn6.29Zn0.23Mg0.07Zr0.04${\rm Fe}_{{\rm 0}{\rm. 03}}^{{\rm 2 +}} $Ca0.01Na0.34)Σ7.01(Ti1.78Nb0.17 Mg0.03Zr0.02)Σ2(Si8.03O24)O2[(OH)3.92F0.08]Σ4F1.00[(H2O)1.18□0.82]Σ2, for Z = 1. Heyerdahlite is triclinic, space group P$\bar 1$, a = 5.392(2), b = 11.968(4), c = 11.868(4) Å, α = 112.743(8), β = 94.816(7), γ = 103.037(8)° and V = 675.6(7) Å3. The crystal structure was refined to R1 = 4.44% for 3577 unique (Fo > 4σF) reflections. In the crystal structure of heyerdahlite, there are four [4]T sites occupied by Si. The [6]D site is occupied mainly by Ti. The T4O12 astrophyllite ribbons composed of SiO4 tetrahedra and D octahedra constitute the H (Heteropolyhedral) sheet. In the O (Octahedral) sheet, there are four Mn-dominant [6]M(1–4) sites. Two H sheets and one central O sheet form the HOH block, and adjacent HOH blocks link via a common ${\rm X}_{\rm D}^{\rm P} $ anion of the two D octahedra. In the I (Intermediate) block between HOH blocks, there are two interstitial cation sites, A and B, and a WA site, partly occupied by H2O. The A site splits into two sites, [12]A(1) and [6]A(2), partly occupied by K and Na, respectively, with A(1)–A(2) = 0.754 Å. The aggregate content of the A site is ideally Na2 apfu. The [10]B site is occupied by Na. The WA site is ideally occupied by (H2O)2 pfu. The mineral is named after the Norwegian explorer Thor Heyerdahl (1914–2002), who was born in Larvik.

High-temperature Fe oxidation coupled with redistribution of framework cations in lobanovite, K2Na(Fe2+4Mg2Na)Ti2(Si4O12)2O2(OH)4– the first titanosilicate case

“…There are plenty of crystalchemical data on heterophyllosilicates at room temperature (see e.g. Sokolova, 2006;Ferraris et al, 2008;Cá mara et al, 2010;Stepanov et al, 2012;Agakhanov et al, 2016;Sokolova & Hawthorne, 2016;Jin et al, 2018;Sokolova et al, 2018), but the same cannot be said of their behaviour at non-ambient conditions.…”