Abstract Bulgakite, ideally Li 2 (Ca,Na)Fe 2+ 7 Ti 2 (Si 4 O 12 ) 2 O 2 (OH) 4 (O,F)(H 2 O) 2 , and nalivkinite, ideally Li 2 NaFe 2+ 7 Ti 2 (Si 4 O 12 ) 2 O 2 (OH) 4 F(H 2 O) 2 , are astrophyllite-supergroup minerals. Bulgakite is a new mineral from the Darai-Pioz alkaline massif in the upper reaches of the Darai-Pioz river, in the area of the joint Turkestansky, Zeravshansky, and Alaisky ridges, Tajikistan. Bulgakite was found in fenitized amphibole–quartz–feldspar rock with brannockite, sogdianite, bafertisite, albite, and titanite. Bulgakite is brownish orange, transparent in thin grains, and has a vitreous luster. Mohs hardness is 3, D meas. = 3.30(2) g/cm 3 , D calc. = 3.326 g/cm 3 . Bulgakite is biaxial (+) with refractive indices (λ = 589 nm) α = 1.695(3), β = 1.711(2), γ = 1.750(3); 2 V meas. = 70(5)°, 2 V calc. = 67°, strong dispersion: r > v . Cleavage is perfect parallel to {001} and moderate parallel to {010}. Chemical analysis by electron microprobe gave SiO 2 35.63, Al 2 O 3 0.95, Na 2 O 1.04, K 2 O 3.27, Cs 2 O 0.31, CaO 2.56, MgO 0.16, ZnO 0.15, FeO 29.24, MnO 7.14, TiO 2 11.07, Nb 2 O 5 0.49, ZrO 2 0.37, SnO 2 1.18, F 1.01, Li 2 O 1.36 (AAS), Rb 2 O 0.85 (AAS), (H 2 O) calc. 4.04, sum 100.38 wt.%, H 2 O was calculated from crystal-structure analysis. The empirical formula based on 31.94 (O + OH + F + H 2 O) pfu is (Li 0.94 K 0.91 Rb 0.12 Cs 0.03 ) Σ2 (Ca 0.60 Na 0.40 ) Σ1 (Fe 2+ 5.34 Mn 1.32 Li 0.25 Mg 0.05 Na 0.04 Zn 0.02 ) Σ7.02 (Ti 1.82 Sn 0.10 Nb 0.05 Zr 0.04 ) Σ2.01 [(Si 7.78 Al 0.24 ) Σ8.02 O 24 ]O 2 (OH) 4 (F 0.70 O 0.30 )[(H 2 O) 0.94 □ 1.06 ] Σ2 , Z = 1. Bulgakite is triclinic, space group P , a 5.374(1), b 11.965(2), c 11.65(3) A, α 113.457(8), β 94.533(8), γ 103.08(1)°, V 657.5(8) A 3 . The six strongest reflections in the X-ray powder diffraction data [ d (A), I, ( hkl )] are: 10.54, 100, (001); 3.50, 100, (003); 2.578, 100, (130); 2.783, 90, (1
2); 1.576, 68, (3
1,
2); 2.647, 55, (
11). The crystal structure has been refined to R 1 = 2.6% for 3592 unique F o > 4σ F ) reflections. In the crystal structure of bulgakite, there are four [4] T sites, with T –O> = 1.626 A, occupied mainly by Si, with minor Al. The TO 4 tetrahedra constitute the T 4 O 12 astrophyllite ribbon. The [6] D site is occupied mainly by Ti, with D –φ> = 1.965 A (φ = O, F). The T 4 O 12 astrophyllite ribbons and D octahedra constitute the H (Heteropolyhedral) sheet. In the O (Octahedral) sheet, there are four Fe 2+ -dominant [6] M (1–4) sites, with = 2.159 A (φ = O, OH). Two H and the central O sheets form the HOH block, and adjacent HOH blocks link via a common anion (X P D ) of two D octahedra. In the I (Intermediate) block between adjacent HOH blocks, there are two interstitial cation sites, A and B , and a W site, partly occupied by H 2 O. The A site splits into two partly occupied sites, [13] A (1) and [6] A (2), with A(1)–A(2) = 1.16 A. The [6] A (2) site is occupied by Li with = 2.285 A (φ = O, F, H 2 O), and the [13] A (1) site is occupied by K, Rb, and Cs with = 3.298 A. The aggregate content of the A site is (Li 0.94 K 0.91 Rb 0.12 Cs 0.03 ) Σ2 , ideally Li 2 apfu . The [10] B site is occupied by (Ca 0.60 Na 0.40 ) with B –φ> = 2.593 A. The W site is occupied by [(H 2 O) 0.94 □ 1.06 ] Σ2 pfu . The mineral is named bulgakite after Lev Vasil9evich Bulgak (born 1955), Russian mineralogist, gemologist, and discoverer of several new minerals. The crystal structure of nalivkinite has been revised and refined to R 1 = 4.52% for 3546 unique ( F o > 4σ F ) reflections: space group P , a 5.374(3), b 11.948(5), c 11.676(5) A, α 113.360(6), β 94.538(8), γ 103.01(1)°, V 658.7(9) A 3 , Z = 1, D calc. = 3.347 g/cm 3 . The revised empirical formula of nalivkinite is based on 32.14 (O + OH + F + H 2 O) pfu : (Li 1.14 K 0.75 Cs 0.09 Pb 0.02 ) Σ2 (Na 0.71 Ca 0.29 ) Σ1 (Fe 2+ 5.62 Mn 0.90 Zr 0.08 Na 0.08 Mg 0.04 Zn 0.04 ) Σ6.76 (Ti 1.56 Nb 0.24 Sn 0.09 Zr 0.08 Ta 0.04 ) Σ2 [(Si 7.86 Al 0.15 ) Σ8.01 O 24 ]O 2 (OH) 4 F[(H 2 O) 1.14 □ 0.86 ] Σ2 . The presence of H 2 O groups in the bulgakite and nalivkinite structures was confirmed by infrared spectroscopy. Bulgakite is a Ca-analogue of nalivkinite. Bulgakite and nalivkinite are related by the following substitution: 0.3 B Ca 2+ + 0.3 X O 2– ↔ 0.3 B Na + + 0.3 X F – .
Two new mineral species, vorontsovite, ideally (Hg5Cu)TlAs4S12, and ferrovorontsovite, ideally (Fe5Cu)TlAs4S12, the Tl- and Tl–Fe-analogues of galkhaite, respectively, have been discovered at the Vorontsovskoe gold deposit, Northern Urals, Russia. They occur as anhedral grains up to 0.5 mm (vorontsovite) and 0.2 mm (ferrovorontsovite) embedded in a calcite-dolomite matrix. The chemical composition of vorontsovite (wt %) is: Hg 35.70, Fe 5.36, Zn 1.26, Cu 3.42, Ag 0.64, Tl 11.53, Cs 0.35, Pb 0.04, As 15.98, Sb 2.35, Te 0.41, S 22.70, Se 0.02, total 99.76. The empirical formula, calculated on the basis of 23 atoms pfu, is: [(Hg3.02Fe1.63Zn0.33)Σ4.98(Cu0.91Ag0.10)Σ1.01](Tl0.96Cs0.04)Σ1.00(As3.62Sb0.33Te0.05)Σ4.00S12.01. The composition of ferrovorontsovite (wt %) is: Hg 25.13, Fe 9.89, Zn 1.16, Cu 3.95, Ag 0.45, Tl 12.93, Cs 0.44, Pb 0.04, As 17.83, Sb 2.15, Te 0.40, S 24.91, total 99.28. The empirical formula, calculated on the basis of 23 atoms pfu, is: [(Fe2.74Hg1.94Zn0.27)Σ4.95(Cu0.96Ag0.06)Σ1.02](Tl0.98Cs0.05)Σ1.03(As3.68Sb0.27Te0.05)Σ4.00S12.00. Both minerals are cubic, space group I-43m, with a = 10.2956(6) Å, V = 1091.3(1) Å3, Z = 2 (vorontsovite); and a = 10.2390(7) Å, V = 1073.43(22) Å3, Z = 2 (ferrovorontsovite). The crystal structures of both minerals were refined to R = 0.0376 (vorontsovite) and R = 0.0576 (ferrovorontsovite). Vorontsovite and ferrovorontsovite have been approved by the IMA-CNMNC under the numbers 2016-076 and 2017-007, respectively. The first one is named after the type locality, but also honors the mining engineer Vladimir Vasilyevich Vorontsov. The second is named for its chemical composition, as the Fe-analogue of the first. Both species are isostructural with galkhaite, being its Tl- and Tl–Fe analogues, respectively, and forming altogether the galkhaite group.
Metahewettite was encountered in hypergene crusts in Paleozoic carbon-silica schists included in the carbon mélange matrix at Hodzha-Rushnai-Mazar in southern Kirgizia.Schist outcrops are marked by multicolored yellow, orange, brown and green crusts of vanadates and sulfates of chalсoalumite group, volborthite, V-bearing phosphates, Cr-V-bearing members of alunite subgroup, members of the pascoite group and vanadium-bronze oxides, including metahewettite.Metahewettite is acicular with individual crystals up to 1 mm in length, and forms radial aggregates 2-3 mm in diameter, or flattened aggregates in narrow fissures.Crystals are dark-brown to reddish-brown with a golden sheen.The crystal structure of metahewettite, Ca(V 5+ 6 O 16 )(H 2 O) 3 , monoclinic, a = 12.208( 5), b = 3.6011(15), c = 18.358(7)Å, β = 118.538(8)°,V = 709.0(8)Å 3 , Z = 2, A2/m, was refined to an R 1 index of 2.4 % based on 1047 unique observed (F o > 4σF) reflections.Electron-microprobe analysis (EDS) showed no detectable constituents apart from Ca and V, and the scattering from each site in the structure is conformable with the ideal composition Ca(V 6 O 16 )(H 2 O) 3 .There are three V sites in the structure with scattering in accord with their complete occupancy by V.The V(1) site is [5]-coordinated by O 2-anions with a distance of 1.823 Å and a [2 + 3] arrangement of vanadyl <1.67 Å> and equatorial (<1.925Å>) bonds.The V(2) and V(3) sites are coordinated by O 2-anions with distances of 1.934 and 1.916 Å and [2 + 2 + 2] and [1 + 4 + 1] arrangements of vanadyl <1.652 Å>, equatorial <1.906 Å> and trans <2.237 Å> bonds, respectively.The V(1) square pyramids share edges and vertices to form chains extending parallel to b with a repeat distance of 3.6 Å.The V(2) and V(3) octahedra share edges and vertices to form ribbons also extending parallel to b.The chains and ribbons link by sharing polyhedron corners to form sheets of V polyhedra parallel to (001).These sheets are linked by interlayer Ca that occupies two interstitial Ca sites, and by (H 2 O) groups.
Abstract A new mineral falgarite, K 4 (V +4 O) 3 (SO 4 ) 5 was discovered at the tract of Kukhi-Malik, Fan-Yagnob coal deposit, ca. 75 km N of Dushanbe, Tajikistan. The new mineral is named after the Falgar, an ancient Sogdian name for an area around the Zeravshan riverhead. Falgarite is a fumarolic mineral formed directly from a gas emitted by a natural underground coal fire. Associated minerals are anhydrite, baryte, molybdite, an unidentified Tl-vanadyl sulfate, K–Mg sulfate and an anhydrous Mg-sulfate. Falgarite forms small isometric or pseudo-octahedral individual crystals (10–60 μm) of turquoise colour and spherical aggregates up to 0.5 mm in diameter. Mohs hardness is ~ 2.5, D meas = 2.87(2) and D calc = 2.89 g/cm 3 . Refractive indices are: α = 1.588(3), β(calc.) = 1.600(3) and γ = 1.609(2) (590 nm). In transmitted light falgarite is transparent green with a weak pleochroism. The mineral is non-soluble in H 2 O and 5% HNO 3 at room temperature. Infrared spectra support the absence of H 2 O and OH – . The chemical composition determined by electron-microprobe analysis is (wt.%): Na 2 O 0.55, K 2 O 20.76, Tl 2 O 1.83, VO 2 29.38 and SO 3 46.78, total 99.29. The empirical formula (based on 23 O apfu) is: (K 3.76 Na 0.15 Tl 0.07 ) Σ3.98 V 3.02 S 4.99 O 23.0 . The strongest lines of the powder X-ray diffraction pattern are [ d ,Å( I ,%)( hkl )]: 3.20(70)(202); 3.17(80)024; 3.14(70) $\bar{2}$ 04; 3.01(50) $\bar{1}$ 51; and 2.88(100)151. Falgarite is monoclinic, P 2 1 / n , a = 8.7209(5), b = 16.1777(6), c = 14.4614(7) Å, β = 106.744(5)°, V = 1953.77(17) Å 3 , Z = 4 and R 1 = 0.05. VO 6 octahedra and SO 4 tetrahedra link together by sharing corners thus forming a [(VO) 3 (SO 4 ) 5 ] 4– framework. K + , Na + and Tl + cations are located in the channels of the framework. The synthetic K 4 (VO) 3 (SO 4 ) 5 analogue is known.
Abstract Rundqvistite-(Ce), ideally Na 3 (Sr 3 Ce)(Zn 2 Si 8 O 24 ), is a new mineral from the Darai-Pioz alkaline massif, Tien-Shan Mountains, Tajikistan. The mineral occurs as elongated grains up to 0.1 mm long and up to 0.03 mm thick embedded in quartz–pectolite aggregate in a silexite-like peralkaline pegmatite. Associated minerals are quartz, fluorite, pectolite, baratovite, aegirine, leucosphenite, neptunite, reedmergnerite, orlovite, sokolovaite, mendeleevite-(Ce), odigitriaite, pekovite, zeravshanite, kirchhoffite and garmite. The mineral is colourless with a vitreous lustre and a white streak, brittle, D meas. is 3.70(2) and D calc. is 3.709 g/cm 3 . Rundqvistite-(Ce) is monoclinic, space group P 2 1 / c , a = 5.1934(16), b = 7.8934(16), c = 26.011(5) Å, β = 90.02(3)° and V = 1066.3(4) Å 3 . The chemical composition of rundqvistite-(Ce) is SiO 2 40.17, La 2 O 3 2.64, Ce 2 O 3 7.55, Pr 2 O 3 0.80, Nd 2 O 3 2.43, Sm 2 O 3 0.33, Eu 2 O 3 0.09, Gd 2 O 3 0.24, Tb 2 O 3 0.18, Dy 2 O 3 0.21, PbO 1.03, SrO 19.83, FeO 0.37, ZnO 13.08, CaO 2.55, Na 2 O 8.04, total 99.54 wt.%. The empirical formula calculated on 24 O apfu (atoms per formula unit) is Na 3.10 Sr 2.29 Ca 0.54 Pb 0.06 (Ce 0.55 La 0.19 Nd 0.17 Pr 0.06 Sm 0.02 Gd 0.02 Eu 0.01 Tb 0.01 Dy 0.01 ) Σ1.04 Zn 1.92 Fe 0.06 Si 8.00 O 24 Z = 2. The structural formula based on refined site-occupancies is (Na 2.94 Sr 0.06 ) Σ3.00 [(Sr 2.23 Ca 0.54 Pb 0.06 Na 0.13 ) Σ2.96 Ln 3+ 1.04 ] Σ4.00 [(Zn 1.92 Fe 2+ 0.06 ) Σ1.98 Si 8 O 24 ], where Ln 3+ 1.04 = (Ce 0.55 La 0.19 Nd 0.17 Pr 0.06 Sm 0.02 Gd 0.02 Eu 0.01 Tb 0.01 Dy 0.01 ) Σ1.04 . The crystal structure of rundqvistite-(Ce) was refined to R 1 = 2.76% on the basis of 3184 unique reflections [ F > 4σ| F |]. In rundqvistite-(Ce), the main structural unit is a (Zn 2 Si 8 O 24 ) 12– sheet parallel to (100). In the sheet, the Si and Zn tetrahedra form four-, five- and eight-membered rings. The interstitial cations at the Na and M (1–3) sites sum to [Na 3 (Sr 3 Ce)] 12– apfu. The Na and M(1–3) polyhedra share common edges to form a layer. Rundqvistite-(Ce) is a structural analogue of vladykinite, ideally Na 3 Sr 4 (Fe 2+ Fe 3+ )Si 8 O 24 . Rundqvistite-(Ce) and vladykinite are related by the following substitution: [8] Ce 3+ + [4] (Zn 2+ ) 2 ↔ [8] Sr 2+ + [4] (Fe 2+ Fe 3+ ). The mineral is named after Dmitry Vasilievich Rundqvist (1930–2022), a prominent Russian geologist and an expert on the geology of ore deposits, metallogeny and mineralogy of Precambrian rocks.
ABSTRACT The hyalotekite group has been approved by the Commission on New Minerals, Nomenclature and Classification of the International Mineralogical Association (memorandum 57–SM/16). The general formula of the minerals of the hyalotekite group may be written as: A 2 B 2 M 2 [Si 8 T 4 O 28 ]W where A = Ba 2+ , Pb 2+ or K + ; B = Ba 2+ , Pb 2+ or K + ; M = Ca 2+ , Y 3+ or REE 3+ ; T = Si 4+ , B 3+ or Be 2+ ; and W = F – or □ (where REE = rare-earth elements and □ = vacancy). Four minerals are currently known in this group: hyalotekite, Ba 4 Ca 2 [Si 8 B 2 (SiB)O 28 ]F, triclinic, I $\bar 1$ ; khvorovite, Pb 2+ 4 Ca 2 [Si 8 B 2 (SiB)O 28 ]F, triclinic I $\bar 1$ ; kapitsaite-(Y), Ba 4 (YCa)[Si 8 B 2 B 2 O 28 ]F, triclinic, I $\bar 1$ ; and itsiite Ba 4 Ca 2 [Si 8 B 4 O 28 ]□, tetragonal, I $\bar 4$ 2 m. We explore the possible end-member compositions within this group by conflating the properties of an end-member with the stoichiometry imposed by the bond topology of the hyalotekite structure-type and the crystal-chemical properties of its known constituents. There are two high-coordination sites in the hyalotekite structure, A and B , and occupancy of each of these sites can be determined only by crystal-structure refinement. If these two sites are considered together, there are 19 end-member compositions of the triclinic structure and six end-member compositions of the tetragonal structure involving A and B = Ba 2+ , Pb 2+ , K + ; M = Ca 2+ , Y 3+ , REE 3+ ; and T = Si 4+ , B 3+ , Be 2+ . There is the possibility for many other hyalotekite-group minerals, and two potential new minerals have been identified from data in the literature.
Abstract Fluorapophyllite-(Cs) (IMA 2018-108a), ideally CsCa4(Si8O20)F(H2O)8, is an apophyllite-group mineral from the moraine of the Darai-Pioz glacier, Tien-Shan, Northern Tajikistan. Associated minerals are quartz, pectolite, baratovite, aegirine, leucosphenite, pyrochlore, neptunite, fluorapophyllite-(K), and reedmergnerite. Fluorapophyllite-(Cs) is a hydrothermal mineral. It is colorless and has a vitreous luster and a white streak. Cleavage is perfect; it is brittle and has a stepped fracture. Mohs hardness is 4.5–5. Dmeas. = 2.54(2) g/cm3, Dcalc. = 2.513 g/cm3. Fluorapophyllite-(Cs) is unixial (+) with refractive indices (λ = 589 nm) ω = 1.540(2), ε = 1.544(2). It is non-pleochroic. Chemical analysis by electron microprobe gave SiO2 48.78, Al2O3 0.05, CaO 22.69, Cs2O 10.71, K2O 1.13, Na2O 0.04, F 1.86, H2Ocalc. 14.61, –O=F2 –0.78, sum 99.09 wt.%; H2O was calculated from crystal-structure analysis. The empirical formula based on 29 (O + F) apfu, H2O = 8 pfu, is (Cs0.75K0.24)Σ0.99(Ca3.99Na0.01)Σ4(Si8.01Al0.01)Σ8.02O20.03F0.97(H2O)8, Z = 2. The simplified formula is (Cs,K)(Ca,Na)4(Si,Al)8O20F(H2O)8. Fluorapophyllite-(Cs) is tetragonal, space group P4/mnc, a 9.060(6), c 15.741(11) Å, V 1292.10(19) Å3. The crystal structure has been refined to R1 = 4.31% based on 498 unique (Fo > 4σF) reflections. In the crystal structure of fluorapophyllite-(Cs), there is one [4]T site occupied solely by Si, <T–O> = 1.615 Å. SiO4 tetrahedra link to form a (Si8O20)8– sheet perpendicular to [001]. Between the Si–O sheets, there are two cation sites: A and B. The A site is coordinated by eight H2O groups [O(4) site], A–O(4) = 3.152(4) Å; the A site contains Cs0.75K0.24□0.01, ideally Cs apfu. The Cs–O bond length of 3.152 Å is definitely larger than the K–O bond length of 2.966–2.971 Å in fluorapophyllite-(K), KCa4(Si8O20)F(H2O)8. The [7]B site contains Ca3.99Na0.01, ideally Ca4apfu; <B–φ> = 2.417 Å (φ = O, F, H2O). The Si–O sheets connect via A and B polyhedra and hydrogen bonding; two H atoms have been included in the refinement. Fluorapophyllite-(Cs) is isostructural with fluorapophyllite-(K). Fluorapophyllite-(Cs) is a Cs-analogue of fluorapophyllite-(K).
Magnesiovesuvianite (IMA 2015-104), ideally Ca 19 Mg(Al,Mg) 12 Si 18 O 69 (OH) 9 , a new vesuvianite-group member, was found in an old museum specimen labelled as vesuvianite from the Tuydo combe, near Lojane, Republic of Macedonia.It occurs as radiating aggregates up to 2 cm across consisting of acicular tetragonal crystals (up to 7 mm long and 5-40 μm thick) with distinct fibre-optic effect.Associated minerals are calcite, grossular-andradite and clinochlore.Single crystals of magnesiovesuvianite are transparent, light pink with a silky lustre.Dominant crystal forms are {100}, {110}, {101} and {001}.The Mohs' hardness is 6.The measured and calculated densities are 3.30(3) and 3.35 g/cm 3 , respectively.Mineral is optically uniaxial, negative, ω = 1.725( 2), ε = 1.721(2).The chemical composition (wt.% electron-microprobe data) is: SiO 2 36.73,Al 2 O 3 20.21,CaO 36.50,MgO 1.80, MnO 0.18, FeO 0.04, Na 2 O 0.01, H 2 O 3.10, total 98.37.The empirical formula based on 19 (Ca + Na) apfu is: (Ca 18.99 Na 0.01 ) Σ19.00 (Mg 0.60 Al 0.40 ) Σ1.00 (Al 11.05 Mg 0.70 Mn 0.07 Fe 0.02 ) Σ11.84 Si 17.84 O 68.72 (OH) 9 .Absorption bands in the IR spectrum are: 393, 412, 443, 492, 576, 606, 713, 802, 906, 968, 1024, 3200, 3450, 3630 cm -1 .The eight strongest lines of the powder X-ray diffraction pattern are (I-d(Å)-hkl): 23-10.96-110, 22-3.46-240,33-3.038-510,100-2.740-432,21-2.583-522,94-2.365-620,19-2.192-710,25-1.6165-672.Magnesiovesuvianite is tetragonal, space group P4/n, unit-cell parameters refined from the powder data are a 15.5026(3), c 11.7858(5), V 2832.4(2)Å 3 , Z = 2.The crystal structure has been refined to R 1 = 0.027 for 3266 unique observed reflections with |F o | ≥ 4σ F .The structure refinements provided scattering factors of the Y1A,B sites close to 12 e -that supports predominant occupancy of these sites by the Mg 2+ cations, in perfect agreement with the 27 Al MAS NMR data.Magnesiovesuvianite is a member of the vesuvianite group with Mg 2+ as a dominant cation at the Y1 site.The name magnesiovesuvianite is given to highlight the species-defining role of Mg.
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