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NALIVKINITE1, Li2nafe2+ a NEW MINERAL of THE New Data on Minerals. М., 2008. Volume 43 5 1 2+ NALIVKINITE , Li2NaFe7 Ti2(Si8O24)O2(OH)4F, A NEW MINERAL OF THE ASTROPHYLLITE GROUP FROM THE DARAI-PIOZ MASSIF, TADJIKISTAN Atali A. Agakhanov Fersman Mineralogical Museum, RAS, Moscow, [email protected] Leonid A. Pautov Fersman Mineralogical Museum, RAS, Moscow, [email protected] Yulia A. Uvarova Queen’s University, Kingston, Ontario, Canada Elena Sokolova University of Manitoba, Manitoba, Winnipeg, Canada Frank C. Hawthorne University of Manitoba, Manitoba, Winnipeg, Canada Vladimir Y. Karpenko Fersman Mineralogical Museum, RAS, Moscow, [email protected] Nalivkinite, a new astrophyllite-group mineral, was discovered in the moraine of the Darai-Pioz alkaline massif located at the intersection of the Zeravshansky, Turkestansky and Alaisky Ridges, Tadjikistan. Nalivkinite occurs in the amphibole-quartz-feldspar rock in association with calcybeborosilite-(Y), bafertisite, jinshajiangite, zircon and thorite. Nalivkinite is brown with a bronze hue and a vitreous luster; in thin plates, it is transparent. Mohs hard- 3 3 ness is 3, Dmeas. = 3.32(2) g/cm , Dcalc. = 3.315 g/cm . It is biaxial positive, np = 1.703(2), nm= 1.716(2), ng =1.745(2), 2Vmeas. = +68(2)°, 2Vcalc. = +68.6°. Nalivkinite is triclinic, space group P1, a = 5.3745(6) Å; b = 11.9299(15) Å; c = 11.6509(14) Å; a =113.325(3)°, b = 94.524(2)°, g = 103.080(2)°, V = 656.2(2) Å3, Z = 1. Cell dimensions refined from X-ray powder diffraction data are as follows: a = 5.3707(2) Å; b = 11.9327(5) Å; c = 11.6546(4) Å; a =113.384(1)°, b = 94.547(1)°, 103.047(1)°, V = 655.85(2) Å3. The strongest reflections in the X-ray powder diffraction powder pattern are as follows: [(d, Å), (I, %), (hkl)]: 10.56 (100) (001), 3.50 (100) (003), 2.780 (80) (1–42), 2.648 (45) (211), 2578 (70)(130), 2.474 (15) (212), 2.295 (30) (131), 2.106 (35) (142), 1.760 (30) (133), 1.660 (15) (0–73). The infrared spectrum of nalivkinite is similar to that of astrophyllite, and the strongest lines are as follows (cm–1): 3600, 1621, 1077(sh), 1056, 975, 929, 696, 649, 566, 441, 438. The chemical composition (electron microprobe, wt. %, Li2O and Rb2O by ICP OES, H2O by the Penfield method): Al2O3 – 0.67, SiO2 – 35.92, TiO2 – 10.50, Nb2O5 – 1.68, CaO – 1.29, MgO – 0.09, MnO – 5.26, FeO – 32.76, Na2O – 1.62, K2O – 2.49, Li2O – 3.76, Cs2O – 1.40, Rb2O – 0.85, H2O – 3.13, F – 0.75, O=F2 – 0.32, total – 100.04. The empirical formula of nalivkinite is 2+ (Li1.03K0.69Cs0.13Rb0.12)1.97(Na0.69Ca0.30)0.99(Fe5.97Mn0.97Mg0.03)6.97(Ti1.72Nb0.16Zr0.08)1.96[Si7.83Al0.17]8O25.98OH4.07 (F0.52OH0.48)1.00 2+ and the ideal formula is Li2NaFe7 Ti2(Si8O24)O2(OH)4F. The crystal structure of nalivkinite was refined to an R1 index of 6.26%. The name honors Dmitry Vasiljevich Nalivkin, a famous Russian geologist (1889–1982), author of numerous works on the geology, stratigraphy and paleontology of Central Asia. The holotype sample of nalivki- nite is deposited at the Fersman Mineralоgical Museum, Russian Academy of Sciences, Moscow. 3 tables, 3 figures, 12 references. Keywords: nalivkinite, astrophyllite lithium analogue, Darai-Pioz alkaline massif. Introduction The astrophyllite group includes nine Minerals of the astrophyllite group have mineral species: the structurally characterized the general formula A2BC7D2T8O26 species astrophyllite, magnesioastrophyllite, [10]–[13] (OH)4X0–1, where A = K, Cs, Rb, H2O, kupletskite (with two polytypes: kupletskite- + [10] [6] H3O , Li, Na and o; B = Na and Ca; C 1А and kupletskite-2М) and niobokuplet- = Fe2+, Fe3+, Mn, Na, Mg and Zn; [6]D = Ti, skite, and the structurally uncharacterized Nb and Zr; [4]T = Si and Al; X = F, OH, O species niobophyllite, cesium-kupletskite and o (Piilonen et al., 2003; Uvarova et al., (recently renamed into a kupletskite-Cs) and 2008). zircophyllite. The minerals of the astrophyllite 1 – Nalivkinite is recommended for the publication by the Commission on New Minerals and Mineral Names of the Russian Mineralogical Society, and was approved by the Commission on New Minerals, Nomenclature and Classification of the International Mineralogical Assosiation on December 4, 2006. 6 New Data on Minerals. М., 2008. Volume 43 group are commonly accessory minerals, but and the lion's share of mineralogical and pet- may be rock-forming minerals in alkaline rographic work has been done on material rocks. There has been much work on the latter collected from glacial debris. The vein rocks occurrence: a detailed review of the 19th and are even less accessible to observation in early 20th Century literature (including the situ, particularly granitic pegmatites, subal- original data on astrophyllite) are given by kaline granitic pegmatites with rare-metal Bonshtedt (1931); later reviews and new data and rare-earth mineralization, reedmergner- are given by Semenov (1972), Macdonald and ite pegmatites, carbonatites, pectolite- Saunders (1973), Piilonen et al. (2003) and microcline-calcite veins, etc. Among the Uvarova et al. (2008). hydrothermally-altered rocks are albitites, Ganzeev et al. (1969) first drew attention aegirine-quartz-microcline-albite rocks with to a deficiency of potassium and enrichment wollastonite, miserite, agrellite, as well as of lithium in astrophyllite from the Darai- fenites. Detailed descriptions are given by Pioz massif: Li, % – 0.59; 0.59; 0.27, equiva- Dusmatov (1968, 1971). lent to 1.27; 1.27; 0.58 wt. % Li2O. Higher An important feature of rocks of the massif contents of lithium (Li2O – 1.30; 1.36 wt. %) is their enrichment in Li. According to in astrophyllite from Darai-Pioz were report- Dusmatov (1971), the following Li (ppm) con- ed by Burova and Dusmatov (1971). Their tents were recorded: biotite granites – 135, work prompted re-investigation of this quartz syenites – 45, aegirine syenites – 70, unusual astrophyllite from Darai-Pioz. cancrinite syenites – 180, fenitized rocks – Accordingly, the Li analogue of astrophyl- 250. There are sixteen Li minerals recorded lite was discovered in rocks from the Upper from the Darai-Pioz massif, seven of which Darai-Pioz massif, and was named nalivki- were discovered there. Indeed, Ganzeev et al. nite in honour of Dmitry Vasiljevich (1969) wrote: “Astrophyllite is a sensitive indi- Nalivkin (1889–1982), participant of the cator of enrichment of Rb, Cs and Li in alka- Pamiro-Tadjik expedition (1920–1930) and line-rock massifs”. These words prove to be author of numerous works on the geology, true for the Darai-Pioz massif. stratigraphy and paleontology of Central Nalivkinite occurs in boulders of the gla- Asia. cial moraine; in-place exposures have not been found. The samples consist of fine- to Occurrence coarse-grained amphibole-quartz-feldspar rock of leucocratic appearance, with a patchy Nalivkinite was found in fenitized rocks texture caused by aggregates of amphibole, of the Upper Darai-Pioz massif by the upper bafertisite, calcybeborosilite-(Y) and nalivki- reaches of the Darai-Pioz river, started from nite. Microcline forms large grayish-yellow the same glacier (Tadjikistan). In plan, the idiomorphic grains 1–8 cm in size, and the massif is slightly elongated in a northwest- albite component does not exceed Ab4, erly direction and adjoins the core of a large although intergrowths of virtually pure albite synclinal fold of С2–3 slates, and the north- are observed. Quartz forms light grey, translu- ern part of the massif an anticlinal fold of cent, sometimes smoky, icy coarse-grained interbedded S1w–S2ld slates and lime- aggregates. Sodic amphibole occurs as pris- stones. The exposed part of the massif con- matic crystals, frequently deformed, up to sists of granites, aegirine and quartz syen- 3 cm long, in which relict aegirine can be ites, and cancrinite foyaites, and covers 18 observed. Fine-grained albite is common. The km2 (Dusmatov, 1971). A significant part of characteristic mineral of nalivkinite-bearing the massif is covered by glaciers and is com- rocks is calcybeborosilite-(Y) which occurs as pletely inaccessible. In the last century, the anhedral dark-grey-to-brown crystals up to 3 glaciers of Central Asia have receded exten- cm in size. There are thick lamellar aggregates sively, and the Darai-Pioz glacier is no of brown-red manganous bafertisite and jin- exception. The receding glacier has left a shajiangite (fig.1), and rectangular pseudo- steep-walled trough valley. Some parts of morphs of fine-grained quartz-calcite-micro- the massif can be seen but close examination cline up to 5–15 mm in size. is not possible without special equipment. There are minor concentrations of dipyra- As a result, knowledge of the massif is, in midal lilac crystals of zircon (1–3 mm), black many respects, rather fragmentary in nature, octahedral crystals of uraniferous pyrochlore 2+ Nalivkinite, Li2NaFe7 Ti2(Si8O24)O2(OH)4F, a new mineral of the astrophyllite group from Darai-Pioz Massif, Tadjikistan 7 Fig. 1. Intergrowth of nalivkinite (Naliv) with jinshajiangite (Jin), pyrochlore (Pyr) and stillwellite-(Ce) (Stil). The BSE image of a polished section (top) and characteristic X-ray maps of the specified elements (bot- tom). (0.5–2 mm), and pinkish-red prismatic crys- Physical properties tals of stillwellite-(Се) from 4 to 10 mm, grains Appearance of nalivkinite is very similar of pale-violet fluorite up to 1 mm, crystals of to that of astrophyllite. In hand specimen, it is pale-green thorite, yellow wedge-shaped brown with a bronze hue; in thin plates, it is crystals of Nb-bearing titanite (Nb2O5 = pale brown and transparent. Cleavage is per- 2.64 wt. %, size <1 mm). Willemite, smithonite fect on (001), good on (010), and imperfect on and barite occur in cavities caused by leaching (100).
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