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Kalyuzhnyite-(Ce), NaKCaSrCeTi(Si8O21)OF(H2O)3, a new mineral from the Darai-Pioz alkaline massif, Tien-Shan mountains, Tajikistan: mineral description, crystal structure and a new double (Si8O21) sheet
- Atali A. Agakhanov, Elena Sokolova, Vladimir Yu. Karpenko, Frank C. Hawthorne, Leonid A. Pautov, Anatoly V. Kasatkin, Igor V. Pekov, Vitaliya A. Agakhanova
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- Journal:
- Mineralogical Magazine / Volume 88 / Issue 1 / February 2024
- Published online by Cambridge University Press:
- 13 October 2023, pp. 19-30
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Kalyuzhnyite-(Ce), ideally NaKCaSrCeTi(Si8O21)OF(H2O)3, is a new mineral from the Darai-Pioz alkaline massif, Tien-Shan mountains, Tajikistan. It occurs as equant grains up to 0.05 × 0.07 mm in a 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, and Dcalc. is 3.120 g/cm3. Kalyuzhnyite-(Ce) is monoclinic, P2/c, a = 18.647(4), b = 11.214(2), c = 14.642(3) Å, β = 129.55(3)° and V = 2360.9(11) Å3. The chemical composition of kalyuzhnyite-(Ce) is Nb2O5 0.53, TiO2 0.16, SiO2 43.85, Er2O3 0.13, Ho2O3 0.10, Gd2O3 0.09, Sm2O3 0.47, Nd2O3 6.22, Pr2O3 1.21, Ce2O3 6.34, La2O3 0.82, PbO 4.90, BaO 0.85, SrO 11.39, CaO 1.86, Cs2O 3.80, K2O 1.59, Na2O 2.99, H2O 5.24, F 1.55, O = F –0.65, total 100.31 wt.%. The empirical formula calculated on 26.11 (O + F) apfu is Na1.07K0.37Cs0.30Sr1.21Ca0.37Pb0.24Ba0.06(Ce0.43Nd0.41Pr0.08La0.06Sm0.03Gd0.01Er0.01Ho0.01)Σ1.04(Ti0.97Nb0.04)Σ1.01Si8.06O25.21F0.90H6.42, Z = 4. The simplified formula is (Na,□)(K,Сs)(Ca,Pb,Sr,Na)SrLn3+Ti(Si8O21)OF(H2O)3, where Ce is the dominant lanthanoid. The crystal structure was solved by direct methods and refined to an R1 index of 2.74%. In kalyuzhnyite-(Ce), the main structural units are a heteropolyhedral Na–Sr–Ce–Ti sheet, ideally [NaSrCeTiOF]7+, and a double (Si8O21)10– sheet parallel to (010). In the Si–O sheet, the Si tetrahedra form ten-membered rings. This is the first occurrence of such a double Si–O sheet in a mineral. The two sheets connect via common vertices of Na-, Sr-, Ce- and Ti-polyhedra and SiO4 tetrahedra to form a framework. The interstitial cations and H2O groups, ideally [(CaK)(H2O)3]3+, occur within the Si–O sheet. The mineral is named in honour of Vasily Avksentievich Kalyuzhny (1899–1993) in recognition of his contributions to the geology of ore deposits of Komi Republic (USSR) and the mineralogy of granitic pegmatites (Tajikistan).
Letnikovite-(Ce), (Na□)Ca2Ce2[Si7O17(OH)]F4(H2O)4, a new mineral from the Darai-Pioz alkaline massif, Tajikistan: mineral description, crystal structure and a new single [Si7O17(OH)] sheet
- Atali A. Agakhanov, Elena Sokolova, Fernando Cámara, Vladimir Yu. Karpenko, Frank C. Hawthorne, Leonid A. Pautov, Anatoly V. Kasatkin, Igor V. Pekov, Vitaliya A. Agakhanova
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- Mineralogical Magazine / Volume 87 / Issue 6 / December 2023
- Published online by Cambridge University Press:
- 09 October 2023, pp. 807-818
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Letnikovite-(Ce), ideally (Na□)Ca2Ce2[Si7O17(OH)]F4(H2O)4, is a new mineral with no natural or synthetic analogues (IMA2022–132). The mineral occurs at the Darai-Pioz alkaline massif, Tien-Shan mountains, Tajikistan, in a silexite-like peralkaline pegmatite. Letnikovite-(Ce) occurs as isolated prismatic grains up to 0.03 × 0.1 mm in a quartz–pectolite aggregate. 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, and Dcalc. is 2.847 g/cm3. Letnikovite-(Ce) is monoclinic, C2/m, a = 7.4726(3), b = 22.9196(9), c = 13.9360(6) Å, β = 105.550(5)° and V = 2299.43(17) Å3. The chemical composition of letnikovite-(Ce) is SiO2 42.38, Gd2O3 0.16, Eu2O3 0.28, Sm2O3 0.07, Nd2O3 5.64, Pr2O3 1.69, Ce2O3 11.73, La2O3 2.24, PbO 1.22, SrO 5.77, FeO 0.32, CaO 11.87, MgO 1.14, Cs2O 0.57, K2O 0.65, Na2O 2.24, H2O 7.79, F 7.29, O = F –3.07, total 99.98 wt.%. The empirical formula calculated on 7 Si apfu is Na0.72K0.14Cs0.04Ca2.10Sr0.55Mg0.28Pb0.05Fe0.04(Ce0.71Nd0.33La0.14Pr0.10Eu0.02Gd0.01)Σ1.31Si7O21.84F3.81H8.58 for Z = 4. The structural formula is (Na0.72Ca0.16□1.12)Σ2(Cs0.04□0.96)Σ1(Ca1.83□0.17)Σ2(Mg0.28Fe0.04□0.68)Σ1(Ln3+1.31Sr0.55Ca0.09Pb0.05)Σ2[Si7O17(OH)]F3.81(H2O)3.79, where Ln3+1.31 = (Ce0.71Nd0.33La0.14Pr0.10Eu0.02Gd0.01)Σ1.31. The simplified formula is (Na,□)2Ca2(Ln3+,Sr)2[Si7O17(OH)]F4(H2O)4, where Ce is the dominant lanthanoid. The crystal structure was solved by direct methods and refined to an R1 index of 4.2%. In letnikovite-(Ce), the main structural unit is a layer which consists of the central heteropolyhedral Ca–Ce sheet and two adjacent single [Si7O17(OH)] sheets parallel to (001). In the Si–O–OH sheet, the Si tetrahedra form five-membered and ten-membered rings. This is the first occurrence of a single [Si7O17(OH)]7– sheet in a mineral. The layers connect via Na and Cs at the interstitial A(1,2) sites, H2O groups and hydrogen bonding. The mineral is named in honour of Felix Artem'evich Letnikov (born October 3rd,1934) in recognition of his outstanding contributions to the field of petrology and geochemistry of Precambrian rocks.
Botuobinskite and mirnyite, two new minerals of the crichtonite group included in Cr-pyrope xenocrysts from the Internatsionalnaya kimberlite
- Dmitriy I. Rezvukhin, Sergey V. Rashchenko, Igor S. Sharygin, Vladimir G. Malkovets, Taisia A. Alifirova, Leonid. A. Pautov, Elena N. Nigmatulina, Yurii V. Seryotkin
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- Mineralogical Magazine / Volume 87 / Issue 3 / June 2023
- Published online by Cambridge University Press:
- 10 February 2023, pp. 433-442
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Two new mineral species of the crichtonite group: botuobinskite, ideally SrFe2+(Ti4+12Cr3+6)Mg2[O36(OH)2] and mirnyite, ideally SrZr(Ti4+12Cr3+6)Mg2O38, occur as inclusions in mantle-derived Cr-pyrope xenocrysts from the Internatsionalnaya kimberlite pipe, Mirny field, Siberian craton. Botuobinskite forms needle- and blade-like acicular crystals up to 1 mm in length and up to 30 μm in diameter, a large platy inclusion (700 × 700 × 80 μm) and roughly isometric grains (up to 80 μm). Mirnyite occurs as needle-and blade-like elongated inclusions (up to 1 mm). Both minerals are jet-black, opaque and exhibit a metallic lustre. In plane-polarised reflected light, botuobinskite and mirnyite are greyish-white with a weak brownish tint. Between crossed polars, the new species show distinct anisotropy in shades of bluish grey to greenish-brown. Neither bireflectance nor pleochroism is observed. Calculated densities for botuobinskite and mirnyite are 4.3582(5) and 4.3867(3) gm/cm3, respectively. The crystal structures of botuobinskite and mirnyite have been refined (R = 0.0316 and 0.0285, respectively) from single crystal X-ray diffraction data. The minerals are trigonal, crystallise in the space group R$\bar{3}$ (No. 148) and are isostructural with other members of the crichtonite group. The unit cell parameters are a = 10.3644(8) Å, c = 20.6588(11) Å and V = 1921.9(2) Å3 for botuobinskite and a = 10.3734(8) Å, c = 20.6910 (12) Å and V = 1928.2(2) Å3 for mirnyite, with Z = 3 for both. The Raman spectra of the minerals show strong peaks at 133, 313 and 711 cm–1. Infrared spectroscopy data for botuobinskite indicates H–O stretching of the hydroxyl groups. Botuobinskite and mirnyite have been approved by the IMA–CNMNC under the numbers 2018-143a and 2018-144a, respectively. Botuobinskite and mirnyite are named after the Botuobinskaya exploration expedition and Mirny town, respectively. The minerals may be considered as crystal-chemical analogues of other crichtonite-group species occurring in the lithospheric mantle (i.e. loveringite, lindsleyite and mathiasite). Both species commonly occur in intimate association with Cr-pyrope as well as other peridotitic minerals and exert an important control on the partitioning of incompatible elements during mantle metasomatism.
Zaykovite, Rh3Se4, a new mineral from the Kazan placer, South Urals, Russia
- Elena V. Belogub, Sergey N. Britvin, Vladimir V. Shilovskikh, Leonid A. Pautov, Vasiliy A. Kotlyarov, Elisaveta V. Zaykova
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- Mineralogical Magazine / Volume 87 / Issue 1 / February 2023
- Published online by Cambridge University Press:
- 16 November 2022, pp. 118-129
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Zaykovite, ideally Rh3Se4, is a new mineral, the first natural rhodium selenide. It was discovered in the assemblages of platinum-group minerals from the Kazan gold placer, South Urals, Russia. The mineral occurs as crystals up to 40 μm in size within the grains of Pt3Fe alloy, in association with unnamed Pd–Sb–Te phase and Au–Pd alloy. In reflected light, zaykovite has a grey colour with bluish-greenish tint; it shows weak bireflectance and anisotropy. Reflectance values [Rmax/Rmin (%) for COM approved wavelengths (nm)] are: 30.1/29.3(470), 32.2/31.0(546), 33.4/32.0(589) and 35.1/33.7(650). The chemical composition corresponds to the empirical formula (Rh2.26Pt0.46Ir0.25Ru0.01Pd0.01Fe0.01)Σ3.00(Se2.77S1.21Te0.02)Σ4.00 Zaykovite is monoclinic, space group C2/m, a = 10.877(1), b = 11.192(1), c = 6.4796(6) Å, β = 108.887(2)°, V = 746.3(1) Å3, Z = 6 and Dcalc = 8.32 g cm–1. The crystal structure has been solved and refined to R1 = 0.016 based on 858 unique observed reflections. The strongest lines of the powder X-ray diffraction pattern [d(Å), (I), (hkl)] are: 5.43(37)($\bar{1}$11), 3.275(75)(310), 3.199(100)($\bar{1}$31), 3.061(87)(002), 2.568(62)(400), 2.545(41)(041), 3.413(34)($\bar{2}$41) and 1.697(34)(441). Zaykovite is a Se analogue of kingstonite, Rh3S4. A continuous series of solid solutions between kingstonite and zaykovite was encountered in the samples from the Kazan placer. The possible sources of this unique Rh–Se mineralisation in the South Urals could be serpentinised dunite–harzburgite or gabbro–clinopyroxenite–dunite complexes in the vicinity.
Ermakovite (NH4)(As2O3)2Br, a new exhalative arsenite bromide mineral from the Fan-Yagnob coal deposit, Tajikistan
- Vladimir Yu. Karpenko, Leonid A. Pautov, Oleg I. Siidra, Mirak A. Mirakov, Anatoly N. Zaitsev, Pavel Yu. Plechov, Saimudasir Makhmadsharif
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- Mineralogical Magazine / Volume 87 / Issue 1 / February 2023
- Published online by Cambridge University Press:
- 14 October 2022, pp. 69-78
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In terrestrial rocks, Br minerals are extremely rare with only nine minerals known where Br is a dominant component. A new arsenite bromide mineral ermakovite, (NH4)(As2O3)2Br, was discovered at the tract of Kukhi-Malik, Fan-Yagnob coal deposit, ca. 75 km N of Dushanbe, Tajikistan. Ermakovite is a fumarolic mineral formed directly from gas from a natural underground coal fire. Associated minerals are sulfur, realgar, amorphous As-sulfides, salammoniac, alacránite, bonazziite and thermessaite-(NH4). In addition, there are amorphous As2S3 intergrowths associated with ermakovite. The mineral typically occurs as tabular or prismatic hexagonal crystals up to 200 μm with the following forms: c (001), m (010) and p (014). Spherulites and multi-twinned intergrowths are very common. The mineral is optically uniaxial (–), ω = 1.960 (5) and ɛ = 1.716(3) (589 nm). The measured density is 3.64(2) g/cm3. The mineral is insoluble in water, HCl, HNO3 and organic solvents. The empirical formula calculated on the basis of (As+Sb) = 4 atoms per formula unit is [(NH4)0.92Na0.01]0.93(As3.94Sb0.06)4.00O6.02(Br0.97Cl0.08I0.01)1.06. The strongest lines in the powder X-ray diffraction pattern are [d, Å (I, %) (hkl)]: 9.160 (80)(001); 4.560(90)(002); 3.228(100) (102); 2.629(80)(110); and 2.522(60)(103). Ermakovite is hexagonal, P6/mmm, a = 5.271(3), c = 9.157(6) Å, V = 220.3(3) Å3 and Z = 1. The sandwich-type structure of ermakovite is based on three types of layers: (1) a honeycomb [As2O3] arsenite layer; (2) an NH4+ layer; and (3) a Br layer. The layer stacking sequence is ⋅⋅⋅NH4–As2O3–Br–As2O3–NH4⋅⋅⋅. Ermakovite has a synthetic analogue. Infrared and Raman spectra are also reported.
An overview of the processes that give rise to high concentrations of Br, leading to the formation of exotic Br minerals, is given.
Falgarite, K4(VO)3(SO4)5, a new mineral from sublimates of a natural underground coal fire at the tract of Kukhi-Malik, Fan-Yagnob coal deposit, Tajikistan
- Leonid A. Pautov, Mirak A. Mirakov, Oleg I. Siidra, Abdulkhak R. Faiziev, Еvgeny V. Nazarchuk, Vladimir Yu. Karpenko, Saimudasir Makhmadsharif
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- Mineralogical Magazine / Volume 84 / Issue 3 / June 2020
- Published online by Cambridge University Press:
- 01 April 2020, pp. 455-462
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A new mineral falgarite, K4(V+4O)3(SO4)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, Dmeas = 2.87(2) and Dcalc = 2.89 g/cm3. 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 H2O and 5% HNO3 at room temperature. Infrared spectra support the absence of H2O and OH–. The chemical composition determined by electron-microprobe analysis is (wt.%): Na2O 0.55, K2O 20.76, Tl2O 1.83, VO2 29.38 and SO3 46.78, total 99.29. The empirical formula (based on 23 O apfu) is: (K3.76Na0.15Tl0.07)Σ3.98V3.02S4.99O23.0. 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, P21/n, a = 8.7209(5), b = 16.1777(6), c = 14.4614(7) Å, β = 106.744(5)°, V = 1953.77(17) Å3, Z = 4 and R1 = 0.05. VO6 octahedra and SO4 tetrahedra link together by sharing corners thus forming a [(VO)3(SO4)5]4– framework. K+, Na+ and Tl+ cations are located in the channels of the framework. The synthetic K4(VO)3(SO4)5 analogue is known.
Akopovaite, Li2Al4(OH)12(CO3)(H2O)3, a new Li member of the hydrotalcite supergroup from Turkestan Range, Kyrgyzstan
- Vladimir Yu. Karpenko, Elena S. Zhitova, Leonid A. Pautov, Atali A. Agakhanov, Oleg I. Siidra, Maria G. Krzhizhanovskaya, Victor A. Rassulov, Vladimir N. Bocharov
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- Mineralogical Magazine / Volume 84 / Issue 2 / April 2020
- Published online by Cambridge University Press:
- 13 February 2020, pp. 301-311
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Akopovaite, ideally Li2Al4(OH)12(CO3)(H2O)3, is a new hydrotalcite-supergroup mineral from the Karasu–Karavshinskoye Sn deposit, Turkestan Range, Kyrgyzstan. It occurs as white or pale yellowish rosette-like aggregates that are composed of tiny curved plates up to 20–30 μm. Akopovaite is associated with gibbsite, quartz, albite, microcline, muscovite, montebrasite, siderite, schorl and birnessite-like Fe–Mn oxides. Akopovaite has a perfect cleavage along {001}, the mineral is transparent and very soft (VHN = 24 that corresponds to Mohs hardness of ca. 1). Dmeas = 2.12(2) g/cm3 and Dcalc = 2.106 g/cm3. The Raman spectra contain bands of carbonate groups and bands of O–H stretching vibrations. The chemical composition (wt.%, electron microprobe for Al and Fe; ICP-OES for Li; CHN method for CO2 and H2O) is Li2O 6.43, Al2O3 45.79, Fe2O3 0.27, CO2 10.09, H2O 36.1, total 98.68. The empirical formula based on (Li + Al + Fe) = 6 apfu is Li1.94(Al4.05Fe0.02)Σ4.07(OH)12(CO3)1.03(H2O)3.03. The crystal structure was refined by the Rietveld method with RB = 0.006 and Rwp = 0.014. Akopovaite is monoclinic, C2/m, a = 5.0953(6), b = 8.877(1), c = 7.806(1) Å, β = 102.572(6)°, V = 344.61(8) Å3 and Z = 1. The polytype should be denoted as 1M. The strongest lines of the powder X-ray diffraction pattern [d, Å (I, %) (hkl)] are: 7.66(100)(001), 4.397(27)(020), 3.821(45)(002,021), 2.4881(27)(200), 2.2273(16)(201) and 1.9027(18)(202). Akopovaite is the first naturally occurring hydrotalcite-supergroup carbonate species of Al and Li; its synthetic analogue is known.
New arsenate minerals from the Arsenatnaya fumarole, Tolbachik volcano, Kamchatka, Russia. X. Edtollite, K2NaCu5Fe3+O2(AsO4)4, and alumoedtollite, K2NaCu5AlO2(AsO4)4
- Igor V. Pekov, Natalia V. Zubkova, Atali A. Agakhanov, Dmitry A. Ksenofontov, Leonid A. Pautov, Evgeny G. Sidorov, Sergey N. Britvin, Marina F. Vigasina, Dmitry Y. Pushcharovsky
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- Mineralogical Magazine / Volume 83 / Issue 4 / August 2019
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- 02 October 2018, pp. 485-495
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Two new isostructural minerals edtollite K2NaCu5Fe3+O2(AsO4)4 and alumoedtollite K2NaCu5AlO2(AsO4)4 have been found in the Arsenatnaya fumarole, Second scoria cone of the Northern Breakthrough of the Great Tolbachik Fissure Eruption, Tolbachik volcano, Kamchatka, Russia. They are associated with sylvite, tenorite, dmisokolovite, shchurovskyite, johillerite, bradaczekite, and orthoclase. Edtollite forms prismatic crystals up to 0.02 mm × 0.1 mm; alumoedtollite forms long-prismatic crystals up to 0.01 mm × 0.1 mm. Both minerals have a semi-metallic lustre. Edtollite is brown–black to black and alumoedtollite is bronze coloured. Dcalc. = 4.26 (edtollite) and 4.28 (alumoedtollite) g cm–3. In reflected light, both minerals are grey, with distinct anisotropy. Reflectance values [edtollite/alumoedtollite: R1–R2, % (λ, nm)] are: 8.3–8.2/8.7–7.7 (470); 7.7–7.4/8.3–7.4 (546); 7.1–6.9/8.3–7.4 (589); and 6.3–6.3/7.6–7.2 (650). Chemical data are: (edtollite/alumoedtollite, wt.%, electron-microprobe): Na2O 3.13/2.58, K2O 8.12/9.09, Rb2O 0.00/0.11, CaO 0.00/0.52, CuO 36.55/38.35, ZnO 0.46/0.00, Al2O3 0.00/3.48, Fe2O3 7.34/1.79, TiO2 0.27/0.00, As2O5 43.57/43.66, total 99.44/99.58. The empirical formulae, based on 18 O apfu, for edtollite is: K1.83Na1.07Cu4.88Zn0.06Fe3+0.98Ti0.04As4.03O18; and for alumoedtollite is: K2.02Rb0.01Na0.87Ca0.10Cu5.06Al0.72Fe3+0.24As3.99O18. Both minerals are triclinic, P$\bar{1}$; unit-cell parameters (edtollite/alumoedtollite) are: a = 5.1168(6)/5.0904(11), b = 9.1241(12)/9.0778(14), c = 9.6979(14)/9.6658(2) Å, α = 110.117(13)/110.334(17), β = 102.454(12)/102.461(19), γ = 92.852(11)/92.788(15)°, V = 411.32(9)/404.88(14) Å3 and Z = 1/1. The strongest reflections in the powder X-ray diffraction pattern [d,Å(I)(hkl)] are for edtollite: 8.79(92)(001), 7.63(41)(0$\bar{1}$1), 5.22(44)(011), 3.427(100)(012), 3.148(64)(0$\bar{1}$3), 2.851(65)($\bar{1}$03) and 2.551(40)($\bar{2}$01); and for alumoedtollite: 8.78(81)(001), 7.62(67)(0$\bar{1}$1), 3.418(100)(012), 3.147(52)(0$\bar{1}$3), 2.558(58)($\bar{1}$22), 2.544(65)($\bar{2}$01) and 2.528(52)($\bar{1}\bar{3}$2). The crystal structures [single-crystal X-ray diffraction, R = 0.0773 (edtollite) and 0.0826 (alumoedtollite); 1504 and 1046 unique reflections, respectively] represent a novel structure type. It is based upon a heteropolyhedral pseudo-framework with the column formed by Cu2+-centred octahedra and square pyramids, octahedra MO6 (M = Fe3+, Al3+ or Cu2+) and AsO4 tetrahedra as the main building unit. K+ and Na+ are located in wide and narrow channels, respectively. Edtollite is named after the Russian geologist and Arctic explorer Eduard Vasilievich Toll (1858–1902), alumoedtollite is its analogue with Al prevailing among trivalent cations.
Rinkite-(Y), Na2Ca4YTi(Si2O7)2OF3, a seidozerite-supergroup TS-block mineral from the Darai-Pioz alkaline massif, Tien-Shan mountains, Tajikistan: Description and crystal structure
- Leonid A. Pautov, Atali A. Agakhanov, Vladimir Yu. Karpenko, Yulia A. Uvarova, Elena Sokolova, Frank C. Hawthorne
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- Mineralogical Magazine / Volume 83 / Issue 3 / June 2019
- Published online by Cambridge University Press:
- 29 June 2018, pp. 373-380
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Rinkite-(Y), ideally Na2Ca4YTi(Si2O7)2OF3, is a new rinkite-group (seidozerite-supergroup) TS-block mineral from the Darai-Pioz alkaline massif, Tian-Shan mountains, Tajikistan. The mineral is of hydrothermal origin. It occurs as aggregates (up to 1.5 cm long) of acicular crystals 0.1–1.0 mm thick, and as separate elongated columnar, flattened-prismatic crystals up to 1 cm long with rectangular or rhombic sections up to 0.5 mm across. Associated minerals are quartz, aegirine, microcline, neptunite, pectolite, calcite, eudialyte-group minerals, fluorite, titanite, turkestanite, kupletskite, galena, albite and pyrochlore-group minerals. Crystals are transparent and colourless to occasionally white, with a vitreous lustre. Rinkite-(Y) has a white streak, uneven, conchoidal fracture and does not fluoresce under a cathode or ultraviolet light. Cleavage is very good on {100}, no parting was observed, Mohs hardness is ~5, and it is brittle, Dmeas. = 3.44(2) g/cm3, Dcalc. = 3.475 g/cm3. It is biaxial (+) with refractive indices (λ = 590 nm) α = 1.662(2), β = 1.666(2), γ = 1.685(5); 2Vmeas. = 50(3) and 2Vcalc. = 49.7°. It is nonpleochroic. Rinkite-(Y) is monoclinic, space group P21/c, a = 7.3934(5), b = 5.6347(4), c = 18.713(1) Å, β = 101.415(2)° and V = 764.2(2) Å3. The six strongest reflections in the X-ray powder diffraction data [d(Å), I, (hkl)] are: 3.057, 100, (006, $\bar{2}$12, 210); 2.688, 28, (016); 9.18, 24, (002); 2.929, 17, ($\bar{2}$13, 211); 3.559, 15, (104, 014) and 2.783, 14, (021). The empirical formula calculated on 18 (O + F) is Na2.11(Ca3.74Sr0.03Mn0.03)Σ3.80(Y0.50Nd0.16Ce0.16Gd0.07Dy0.06Sm0.05Pr0.03La0.03${\rm U}_{0.01}^{{\rm 4 + }} {\rm )}_{\Sigma 1.07}{\rm (T}{\rm i}_{0.85}{\rm N}{\rm b}_{0.17}{\rm W}^{6+}_{0.01}{\rm T}{\rm a}_{0.01}{\rm )}_{\Sigma 1.04}\left( {{\rm S}{\rm i}_{4.03}{\rm O}_{14}} \right){\rm O}_{1.40}{\rm F}_{2.60}$ with Z = 2. The ideal formula is Na2Ca4YTi(Si2O7)2OF3. The crystal structure was refined on a twinned crystal to R1 = 4.59% on the basis of 1489 unique reflections (F > 4σF) and is a framework of TS (Titanium-Silicate) blocks. The TS block consists of HOH sheets (H – heteropolyhedral, O – octahedral) parallel to (100). In the O sheet, the Ti-dominant [6]MO1 site ideally gives 1 Ti apfu. The [8]MO2 and [6]MO3 sites are ideally occupied by Na and (NaCa) apfu. In the H sheet, the [7]MH site is occupied by Ca1.13Y0.50REE0.37, (REE = rare-earth element), ideally (CaY), <MH–φ> = 2.415 Å and the [7]AP site is occupied by Ca1.81REE0.19, ideally Ca2, <AP–φ> = 2.458 Å. The MH + AP sites ideally give (Ca3Y) apfu. The MH and AP polyhedra and Si2O7 groups constitute the H sheet. Linkage of H and O sheets via common vertices of MH and AP polyhedra and Si2O7 groups with MO1–3 polyhedra results in a TS block. The TS block in rinkite-(Y) exhibits linkage 1 and stereochemistry typical for the rinkite group (Ti = 1 apfu) of the seidozerite supergroup. For rinkite-(Y), the ideal structural formula of the form AP2MH2MO4(Si2O7)2$ \left( {{\rm X}_{\rm M}^{\rm O} } \right)_2\left( {{\rm X}_{\rm A}^{\rm O} } \right)_2{\rm is }\;\left( {{\rm C}{\rm a}_3{\rm Y}} \right){\rm Na}\left( {{\rm NaCa}} \right){\rm Ti}\left( {{\rm S}{\rm i}_2{\rm O}_7} \right)_2\left( {{\rm OF}} \right){\rm F}_2 $ with Z = 2. The mineral is named rinkite-(Y) as it is structurally identical to rinkite-(Ce) and Y is the dominant rare-earth element.
Chemographic exploration of the hyalotekite structure-type
- Frank C. Hawthorne, Elena Sokolova, Atali A. Agakhanov, Leonid A. Pautov, Vladimir Yu. Karpenko, Edward S. Grew
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- Mineralogical Magazine / Volume 82 / Issue 4 / August 2018
- Published online by Cambridge University Press:
- 28 February 2018, pp. 929-937
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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: A2B2M2[Si8T4O28]W where A = Ba2+, Pb2+ or K+; B = Ba2+, Pb2+ or K+; M = Ca2+, Y3+ or REE3+; T = Si4+, B3+ or Be2+; and W = F– or □ (where REE = rare-earth elements and □ = vacancy).
Four minerals are currently known in this group: hyalotekite, Ba4Ca2[Si8B2(SiB)O28]F, triclinic, I$\bar 1$; khvorovite, Pb2+4Ca2[Si8B2(SiB)O28]F, triclinic I$\bar 1$; kapitsaite-(Y), Ba4(YCa)[Si8B2B2O28]F, triclinic, I$\bar 1$; and itsiite Ba4Ca2[Si8B4O28]□, tetragonal, I$\bar 4$2m.
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 = Ba2+, Pb2+, K+; M = Ca2+, Y3+, REE3+; and T = Si4+, B3+, Be2+. There is the possibility for many other hyalotekite-group minerals, and two potential new minerals have been identified from data in the literature.
Odigitriaite, CsNa5Ca5[Si14B2O38]F2, a new caesium borosilicate mineral from the Darai-Pioz alkaline massif, Tajikistan: Description and crystal structure
- Atali A. Agakhanov, Leonid A. Pautov, Elena Sokolova, Frank C. Hawthorne, Vladimir Yu Karpenko, Oleg I. Siidra, Vyacheslav A. Muftakhov
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- Mineralogical Magazine / Volume 81 / Issue 1 / February 2017
- Published online by Cambridge University Press:
- 02 January 2018, pp. 113-122
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Odigitriaite, a new Cs, Na, Ca borosilicate mineral, was discovered in moraine adjacent to the Darai-Pioz alkaline massif in the upper reaches of the Darai-Pioz river at the intersection of the Turkestansky, Zeravshansky and Alaisky mountain ridges, Tajikistan. It occurs as irregular thin flakes associated with quartz, pectolite, baratovite, fluorite, pekovite, polylithionite, aegirine, leucosphenite, pyrochlore, neptunite, reedmergnerite, mendeleevite-(Ce), zeravshanite and sokolovaite. It is colourless with a white streak, is translucent and has a vitreous lustre; it does not fluoresce under ultraviolet light. Odigitriaite is brittle with an uneven fracture and a Mohs hardness of 5. The calculated density is 2.80(2) g/cm3. The indices of refraction are α = 1.502, β = 1.564, γ = 1.576; 2Vobs = 46(2)°, dispersion is weak r > v, and there is no pleochroism. The chemical composition is as follows (electron microprobe, H2O calculated from structure): SiO2 55.30, Al2O3 0.09, Y2O3 0.44, MnO 0.94, FeO 0.10, PbO 0.21, K2O 0.01 Cs2O 8.36, B2O3 4.75, H2O 0.37, F 1.74, O = F2 –0.74, total 99.43 wt.%. The empirical formula of odigitriaite is Cs0.90Na5.12Ca4.68Mn0.20Y0.06Fe0.02Pb0.01[Si13.92Al0.03B2.06O38]F1.39(OH)0.62. The end-member formula is CsNa5Ca5[Si14B2O38]F2. The strong reflections in the powder X-ray diffraction pattern are: [(d, Å), (I, %), (hkl)]: 5.45 (25) (1 1 3), 4.66 (33) (3 1 1), 4.40 (26) (0 2 2), 4.10 (36) (3 1 3), 3.95 (25) (3̄ 1 3), 2.85 (31) (2 2 2), 2.68 (40) (0 0 6), 3.62 (45) (0 2 4), 3.35 (100) (2̄ 2 4), 3.31 (30) (3̄ 1 5), 3.25 (35) (4 0 4), 3.04 (60) (4̄ 2 2), 2.925 (22) (4̄ 2 3), 1.813 (23) (9 1 0). Odigitriaite is monoclinic, space group C2/c, a = 16.652(5), b = 9.598 (3), c = 22.120(7) Å, β= 92.875(14)°, V = 3530.9(1.9) Å3, Z = 4. The crystal structure of odigitriaite was solved by direct methods and refined to an R 1 value of 2.75% based on single-crystal X-ray data. It is a double-layer sheet-borosilicate mineral; Cs and Na are intercalated within the double-layer sheet, and the double layers are linked by interstitial Ca and Na atoms.
Khvorovite, Pb2+4Ca2[Si8B2(SiB)O28]F, a new hyalotekite-group mineral from the Darai-Pioz alkaline massif, Tajikistan: Description and crystal structure
- Leonid A. Pautov, Atali A. Agakhanov, Elena Sokolova, Frank C. Hawthorne, Vladimir Y. Karpenko, Oleg I. Siidra, Viktor K. Garanin, Yassir A. Abdu
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- Mineralogical Magazine / Volume 79 / Issue 4 / August 2015
- Published online by Cambridge University Press:
- 02 January 2018, pp. 949-963
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Khvorovite, ideally Pb42+Ca2[Si8B2(SiB)O28]F, is a new borosilicate mineral of the hyalotekite group from the Darai-Pioz alkaline massif in the upper reaches of the Darai-Pioz river, Tajikistan. Khvorovite was found in a pectolite aggregate in silexites (quartz-rich rocks). The pectolite aggregate consists mainly of pectolite, quartz and fluorite, with minor aegirine, polylithionite, turkestanite and baratovite; accessory minerals are calcite, pyrochlore-group minerals, reedmergnerite, stillwellite-(Ce), pekovite, zeravshanite, senkevichite, sokolovaite, mendeleevite-(Ce), alamosite, orlovite, leucosphenite and several unknown Cs-silicates. Khvorovite occurs as irregular grains, rarely with square or rectangular sections up to 150 μm, and grain aggregates up to 0.5 mm. Khvorovite is colourless, rarely white, transparent with a white streak, has a vitreous lustre and does not fluoresce under ultraviolet light. Cleavage and parting were not observed. Mohs hardness is 5–5.5, and khvorovite is brittle with an uneven fracture. The measured and calculated densities are 3.96(2) and 3.968 g/cm3, respectively. Khvorovite is biaxial (+) with refractive indices (λ = 589 nm) α = 1.659(3), βcalc. = 1.671(2), γ = 1.676(3); 2Vmeas. = 64(3)°, medium dispersion: r < v. Khvorovite is triclinic, space group I1¯, a = 11.354(2), b = 10.960(2), c = 10.271(2) Å, α = 90.32(3), β = 90.00(3), γ = 90.00(3)°, V = 1278(1) Å3, Z = 2. The six strongest lines in the powder X-ray diffraction pattern [d (Å), I, (hkl)] are: 7.86, 100, (110); 7.65, 90, (101); 7.55, 90, (011); 3.81, 90, (202); 3.55, 90, (301); 2.934, 90, (312, 312). Chemical analysis by electron microprobe gave SiO2 36.98, B2O3 6.01, Y2O3 0.26, PbO 40.08, BaO 6.18, SrO 0.43, CaO 6.77, K2O 1.72, Na2O 0.41, F 0.88, O=F –0.37, sum 99.35 wt.%. The empirical formula based on 29 (O+F) a.p.f.u. is (Pb2.762+Ba0.62K0.56Na0.16)Σ4.10(Ca1.86Sr0.06Y0.04Na0.04)Σ2[Si8B2(Si1.46B0.65)Σ2.11O28](F0.71O0.29), Z = 2 , and the simplified formula is (Pb2+, Ba, K)4Ca2[Si8B2(Si,B)2O28]F. The crystal structure of khvorovite was refined to R1 = 2.89% based on 3680 observed reflections collected on a four-circle diffractometer with MoKα radiation. In the crystal structure of khvorovite, there are four [4]-coordinated Si sites occupied solely by Si with <Si–O>= 1.617 Å. The [4]-coordinated B site is occupied solely by B, with <B–O> = 1.478 Å. The [4]-coordinated T site is occupied by Si and B (Si1.46B0.54), with <T–O> = 1.605 Å; it ideally gives (SiB) a.p.f.u. The Si, B and T tetrahedra form an interrupted framework of ideal composition [Si8B2(SiB)O28]11–. The interstitial cations are Pb2+, Ba and K (minor Na) [A(11–22) sites] and Ca [M site]. The two A sites are each split into two subsites ∼0.5 Å apart and occupied by Pb2+ and Ba + K. The [8]-coordinated M site is occupied mainly by Ca, with minor Sr, Y and Na. Khvorovite is a Pb2+ analogue of hyalotekite, (Ba,Pb2+,K)4(Ca,Y)2[Si8(B,Be)2(Si,B)2O28]F and a Pb2+-, Ca-analogue of kapitsaite-(Y), (Ba,K)4(Y,Ca)2[Si8B2(B,Si)2O28]F. It is named after Pavel V. Khvorov (b. 1965), a Russian mineralogist, to honour his contribution to the study of the mineralogy of the Darai-Pioz massif.
Mendeleevite-(Nd), (Cs,□)6 (□,Cs)6 (□,K)6 (REE,Ca)30(Si70O175)(OH,H2O,F)35, a new mineral from the Darai-Pioz alkaline massif, Tajikistan
- Atali A. Agakhanov, Leonid A. Pautov, Elena Sokolova, Frank C. Hawthorne, Vladimir Yu Karpenko, Oleg I. Siidra, Viktor K. Garanin
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- Mineralogical Magazine / Volume 81 / Issue 1 / February 2017
- Published online by Cambridge University Press:
- 02 January 2018, pp. 135-141
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Mendeleevite-(Nd), (Cs,□)6(□,Cs)6(□,K)6(REE,Ca)30(Si70O175)(OH,H2O,F)35 is a new mineral from the Darai-Pioz alkaline massif, Tajikistan. Mendeleevite-(Nd) was found in a pectolite aggregate in silexites (quartz-rich rocks) which consist of fine to medium pectolite grains, quartz, aegirine and fluorite, with minor khvorovite, mendeleevite-(Ce), sokolovaite, hyalotekite, orlovite, kirchhoffite, pekovite, neptunite, zeravshanite, senkevichite, nordite-(Nd), alamosite, pyrochlore-group minerals and baratovite. Mendeleevite-(Nd) forms colourless cubic crystals 10–40 μm in size; it has a vitreous lustre and a Mohs hardness of 5–5.5; Dmeas. = 3.20(2) g/cm3, Dcalc. = 3.155 g/cm3. Mendeleevite-(Nd) is optically isotropic, with the refractive index n = 1.582(2). Mendeleevite-(Nd) is cubic, space group Pm3̄, a = 21.9106(4) Å; Z = 2. The six strongest reflections in the powder X-ray diffraction pattern are [d (Å), I (%), (h k l)] are: 11.01, 100, (0 0 2); 15.63, 55, (0 1 1); 3.47, 42, (2 0 6); 3.099, 42, (3 4 5); 2.192, 42, (0 0 10); 1.819, 41, (3 6 10). Chemical analysis by electron microprobe gave SiO2 42.30, Ce2O3 10.12, La2O3 3.60, Nd2O3 16.19, Pr2O3 2.79, Sm2O3 4.19, Gd2O3 1.69, Eu2O3 0.47, SrO 2.99, CaO 2.20, Cs2O 8.50, K2O 0.85, H2O 3.85, F 1.25, –O = F2 –0.53, sum 100.46 wt.%, with H2O calculated by analogy with mendeleevite-(Ce). The empirical formula based on 210 (O + F) apfu, with F + OH + H2O = 35 pfu, is Cs6(□4.20K1.80)∑6{[(Nd9.57Ce6.13Sm2.39La2.20Pr1.68Gd0.93Eu0.27)∑23.17(Ca3.90Sr2.87)∑6.77]∑29.94□0.06}∑30(Si70.03O175)(OH14.47F6.54)∑21.01 (H2O)14, Z = 2. The simplified and ideal formulae are (Cs,□)6 (□,Cs)6(□,K)6 (REE,Ca)30 (Si70O175)(OH, H2O,F)35 and Cs6(REE23Ca7)(Si70O175)(OH,F)19(H2O)16, respectively. The compatibility index (from measured density) = – 0.039 (excellent). Mendeleevite-(Nd) is a Nd analogue of mendeleevite-(Ce), (Cs,□)6(□,Cs)6(□,K)6(REE,Ca,□)30(Si70O175)(H2O,OH,F,□)35. Both minerals are named after Dmitri Mendeleev (1834–1907), the great Russian chemist, author of the periodic table of chemical elements, who has had a significant impact on the development of natural sciences and industry, both in Russia and around the world.