Natrophosphate, Arctic Mineral and Nuclear Waste Phase: Structure Refinements and Chemical Variability

The crystal structures of natural (Mt. Koashva, Khibiny alkaline massif, Kola Peninsula, Russian Arctic) and synthetic (obtained from an aqueous solution of sodium phosphate and sodium fluoride (1:1) by evaporation at room temperature (RT)) natrophosphate, Na7(PO4)2F·19H2O, have been investigated using single-crystal X-ray diffraction analysis. Natrophosphate and its synthetic analogue are cubic, Fd-3c, a = 27.6942(3) Å (natrophosphate at RT), a = 27.6241(4) Å (natrophosphate at 100 K), a = 28.1150(12) Å (synthetic analogue at RT), a = 27.9777(7) Å (synthetic analogue at 100 K). The crystal structure is based upon the super-octahedral [Na6(H2O)18F]5+ polycationic complexes consisting of six edge-linked Na6(OH2)5F octahedra sharing one common fluorine vertex. The A site is statistically occupied by Na and H2O with the prevalence of H2O with the refined occupancy factors O:Na equal to 0.53:0.47 for natrophosphate and 0.75:0.25 for its synthetic analogue. The coordination of the A site in synthetic natrophosphate is enlarged compared to the natural sample, which agrees well with its higher occupancy by H2O molecules. The general formula of natrophosphates can be written as Na6+xHxF(PO4)2·(19 + x)H2O, where x = 0–1. The chemical variability of natrophosphate allows to explain the discrepancies in its solubility reported by different authors. The information-based parameters of structural complexity are equal to 3.713 bit/atom and 2109.177 bit/cell that allows to classify natrophosphate as a structurally very complex mineral.

Chirvinskyite, (Na,Ca)13(Fe,Mn,□)2(Ti,Nb)2(Zr,Ti)3-(Si2O7)4(OH,O,F)12, a New Mineral with a Modular Wallpaper Structure, from the Khibiny Alkaline Massif (Kola Peninsula, Russia)

Chirvinskyite, (Na,Ca)13(Fe,Mn,□)2(Ti,Nb)2(Zr,Ti)3(Si2O7)4(OH,O,F)12, is a new wöhlerite–related zirconotitano–sorosilicate. It is triclinic, P1, a = 7.0477(5), b = 9.8725(5), c = 12.2204(9) Å, α = 77.995(5), β = 82.057(6), γ = 89.988(5)°, V = 823.35(9) Å3, Z = 1. The mineral was found in albitized alkaline pegmatites in a foyaite of the Mt. Takhtarvumchorr (Khibiny alkaline massif, Kola Peninsula, Russia, N 67°40’, E 33°33’). Chirvinskyite forms sheaf–like and radiated aggregates (up to 6 mm in diameter) of split fibrous crystals hosted by saccharoidal fluorapatite and albite. The mineral is pale cream in color, with a silky luster and a white streak. The cleavage is not recognized. Mohs hardness is 5. Chirvinskyite is biaxial (–), α 1.670(2), β 1.690(2), γ 1.705(2) (589 nm), 2Vcalc = 80.9°. The calculated and measured densities are 3.41 and 3.07(2) g·cm−3, respectively. The empirical formula based on Si = 8 apfu is (Na9.81Ca3.28K0.01)∑13.10(Fe0.72Mn0.69□0.54Mg0.05)∑2.00 (Ti1.81Nb0.19)∑2.00(Zr2.27Ti0.63)∑2.90(Si2O7)4{(OH)5.94O3.09F2.97}∑12.00. Chirvinskyite belongs to a new structure type of minerals and inorganic compounds and is related to the wöhlerite-group minerals. Its modular “wallpaper” structure consists of disilicate groups Si2O7 and three types of “octahedral walls”. The mineral is named in honor of Petr Nikolaevich Chirvinsky (1880–1955), Russian geologist and petrographer, head of the Petrography Department of the Perm’ State University (1943–1953), for his contributions to mineralogy and petrology, including studies of the Khibiny alkaline massif.

Vanadium Mineralization in the Kola Region, Fennoscandian Shield

In the northern Fennoscandian Shield, vanadium mineralization occurs in the Paleoproterozoic Pechenga–Imandra-Varzuga (PIV) riftogenic structure. It is localized in sulfide ores hosted by sheared basic and ultrabasic metavolcanics in the Pyrrhotite Ravine and Bragino areas and was formed at the latest stages of the Lapland–Kola orogeny 1.90–1.86 Ga ago. An additional formation of vanadium minerals was derived from contact metamorphism and metasomatism produced by the Devonian Khibiny alkaline massif in the Pyrrhotite Ravine area. Vanadium forms its own rare minerals (karelianite, coulsonite, kyzylkumite, goldmanite, mukhinite, etc.), as well as occurring as an isomorphic admixture in rutile, ilmenite, crichtonite group, micas, chlorites, and other minerals. Vanadium is inferred to have originated from two sources: (1) basic and ultrabasic volcanics initially enriched in vanadium; and (2) metasomatizing fluids that circulated along shear zones. The crystallization of vanadium and vanadium-bearing minerals was accompanied by chromium and scandium mineralization. Vanadium mineralization in Paleoproterozoic formations throughout the world is briefly considered. The simultaneous development of vanadium, chromium and scandium mineralizations is a unique feature of the Kola sulfide ores. In other regions, sulfide ores contain only two of these three mineralizations produced by one ore-forming process.

Vanadium mineralization in the Kola region, Fennoscandian Shield

In the northern Fennoscandian Shield, a vanadium mineralization occurs in the Paleoproterozoic Pechenga–Imandra-Varzuga (PIV) riftogenic structure. It is localized in sulfide ores hosted by sheared basic and ultrabasic metavolcanics in the Pyrrhotite Ravine and Bragino areas and was formed at the latest stages of the Lapland-Kola orogeny 1.90–1.86 Ga ago. An additional formation of vanadium minerals derived from contact metamorphism and metasomatism produced by the Devonian Khibiny alkaline massif in the Pyrrhotite Ravine area. Vanadium forms its own rare minerals (karelianite, coulsonite, kyzylkumite, goldmanite, mukhinite, etc.), as well as it can be an isomorphic admixture in rutile, ilmenite, crichtonite group, micas, chlorites, etc. Vanadium originated from two sources: (1) basic and ultrabasic volcanics initially enriched in vanadium and (2) metasomatizing fluids that circulated along shear zones. The crystallization of vanadium and vanadium-bearing minerals was accompanied by chromium and scandium mineralization. Vanadium mineralization in Paleoproterozoic formations throughout the world is briefly considered. The simultaneous development of vanadium, chromium and scandium mineralizations is a unique feature of the Kola sulfide ores. In other regions sulfide ores contain only two of these three mineralizations produced by one ore-forming process.

Lobanovite, K2Na(Fe42+Mg2Na)Ti2(Si4O12)2O2(OH)4, a new mineral of the astrophyllite supergroup and its relation to magnesioastrophyllite

Lobanovite, K2Na(Fe42+Mg2Na)Ti2(Si4O12)2O2(OH)4, is a new mineral of the astrophyllite supergroup from Mt. Yukspor, the Khibiny alkaline massif, Kola Peninsula Russia. It has been known previously under the following names: monoclinic astrophyllite, magnesium astrophyllite, magnesiumastrophyllite and magnesioastrophyllite but has never been formally proposed and approved as a valid mineral species by the Commission on new Minerals, Nomenclature and Classification of the International Mineralogical Association. It has now been revalidated and named lobanovite after Dr. Konstantin V. Lobanov, a prominent Russian ore geologist who worked in the Kola Peninsula for more than forty years (Nomenclature voting proposal 15-B). Lobanovite has been described from pegmatitic cavities on Mt. Yukspor where it occurs as elongated bladed crystals, up to 0.04 mm wide and 0.2 mm long, with a straw yellow to orange colour. Associated minerals are shcherbakovite, lamprophyllite, delindeite, wadeite, umbite and kostylevite. Lobanovite is biaxial (–) with refractive indices (λ = 589 nm) α = 1.658, βcalc. = 1.687, γ = 1.710; 2Vmeas. = 81.5– 83°. Lobanovite is monoclinic, space group C2/m, a = 5.3327(2), b = 23.1535(9), c = 10.3775(4) Å, β = 99.615(1)°, V = 1263.3 (1) Å 3, Z = 2. The six strongest reflections in the powder X-ray diffraction data [d (Å), I, (hkl)] are: 3.38, 100, (003); 2.548, 90, (063); 10.1, 80, (001); 3.80, 60, (042,131); 3.079, 50, (132,062); 2.763, 90, (1̄71). The chemical composition of lobanovite was determined by electron-microprobe analysis and the empirical formula (K1.97Ba0.01)∑1.98(Na0.65Ca0.14)∑0.79 (Fe3.182+Mg2.02Na1.00Mn0.72)∑6.92(Ti1.99Nb0.06)∑2.05[(Si8.01Al0.06)∑8.07O24]O2(OH)4.03F0.19 was calculated on the basis of 30.2 (O + OH + F) anions, with H2O calculated from structure refinement, Dcalc. = 3.161 g cm–3. In the structure of lobanovite, the main structural unit is the HOH block, which consists of one close-packed O (Octahedral) and two H (Heteropolyhedral) sheets. The M(1–4) octahedra form the O sheet and the T4O12 astrophyllite ribbons and [5]-coordinated Ti-dominant D polyhedra link through common vertices to form the H sheet. The HOH blocks repeat along [001], and K and Na atoms occur at the interstitial A and B sites. The simplified and end-member formulae of lobanovite are K2Na [(Fe2+,Mn)4Mg2Na]Ti2(Si4O12)2O2(OH)4 and K2Na(Fe42+Mg2Na)Ti2(Si4O12)2O2(OH)4, respectively.