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4F, a New Astrophyllite-Super- Group Mineral from Mont Saint-Hilaire, Quebec,´ Canada

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4F, a New Astrophyllite-Super- Group Mineral from Mont Saint-Hilaire, Quebec,´ Canada 201 The Canadian Mineralogist Vol. 57, pp. 201-213 (2019) DOI: 10.3749/canmin.1800071 LAVEROVITE, K2NaMn7Zr2(Si4O12)2O2(OH)4F, A NEW ASTROPHYLLITE-SUPER- GROUP MINERAL FROM MONT SAINT-HILAIRE, QUEBEC,´ CANADA § ELENA SOKOLOVA ,MAXWELL C. DAY, AND FRANK C. HAWTHORNE Department of Geological Sciences, University of Manitoba, Winnipeg, Manitoba R3T 2N2 Canada ANATOLY V. KASATKIN Fersman Mineralogical Museum, Russian Academy of Sciences, Leninskii Prospekt, 18-2, 119071 Moscow, Russia ROBERT T. DOWNS Department of Geosciences, University of Arizona, 1040 E 4th Street, Tucson, Arizona 85721-0077, USA LA´ SZLO´ HORVATH´ AND ELSA PFENNINGER-HORVATH´ 594 Main Road, Hudson Heights, Quebec´ J0P 1J0, Canada ABSTRACT Laverovite (IMA 2017-009b), ideally K2NaMn7Zr2(Si4O12)2O2(OH)4F, is a kupletskite-group (astrophyllite-supergroup) mineral from Mont Saint-Hilaire, Quebec,´ Canada. Associated minerals are zircophyllite, kupletskite, astrophyllite, aegirine, analcime, orthoclase, and albite. Laverovite is brown, transparent in thin grains, and has a vitreous luster. Mohs hardness is 3, 3 Dcalc. ¼ 3.367 g/cm . Laverovite is biaxial (–) with refractive indices (k ¼ 589 nm) a ¼ 1.670(2), b ¼ 1.710(5), c ¼ 1.740(5); 2Vmeas. ¼ 82(2)8,2Vcalc. ¼ 808, strong dispersion: r . v. Cleavage is perfect parallel to {001}. Chemical analysis by electron microprobe gave Nb2O5 0.56, ZrO2 9.78, TiO2 4.69, SiO2 33.52, Al2O3 0.94, SrO 0.13, ZnO 0.07, FeO 13.94, MnO 20.51, CaO 0.48, MgO 0.76, Cs2O 0.05, K2O 6.00, Na2O 2.28, F 1.80, H2Ocalc. 2.57, sum 97.32 wt.%; H2O was calculated from crystal-structure analysis. The empirical formula based on 31.15 (O þ F) apfu with [OH þ F ¼ 5 pfu and H2O ¼ 0.15 pfu] 2þ is (K1.78Sr0.02Cs0.01A0.19)R2(A1.85Na0.15)R2(Na0.88Ca0.12)R1(Mn4.03Fe 2.71Mg0.25Zn0.01)R7(Zr1.11Ti0.82Nb0.06Mg0.01)R2[(Si7.78 2þ Al0.26)R8.04O24]O2[(OH)3.68F0.32]R4F[A1.85(H2O)0.15]R2, Z ¼ 1. The simplified formula is K2Na(Mn,Fe )7(Zr,Ti)2(Si4O12)2O2 ˚ (OH)4F. Laverovite is triclinic, space group P1, a 5.4329(1), b 11.9232(3), c 11.7491(3) A, a 112.905(2), b 94.696(1), c 103.178(1)8, V 670.14(5) A˚ 3. The six strongest lines in the X-ray powder diffraction data [d (A˚ )(I)(hkl)] are: 3.452(92)(003,111); 2.788(97)ð131; 142Þ; 2.680(68)ð211Þ; 2.589(100)ð130; 143Þ; 2.504(44)ð212Þ, and 1.590(50)ð351; 322Þ. The crystal structure has been refined to R1 ¼ 3.26% for 3757 observed (Fo . 4rF) reflections. In the crystal structure of [4] ˚ laverovite, there are four T sites, with ,T–O. ¼ 1.621 A, occupied mainly by Si, with minor Al. TO4 tetrahedra constitute [6] the T4O12 astrophyllite ribbon. The Zr-dominant D site is occupied mainly by Zr and Ti and minor Nb and Mg, with ,D–u. ˚ ¼ 2.002 A (u ¼ O, F). The T4O12 astrophyllite ribbons and D octahedra constitute the H (Heteropolyhedral) sheet. In the O (Octahedral) sheet, there are four Mn2þ-dominant [6]M(1–4) sites, with ,M(1–4)–u. ¼ 2.187, 2.174, 2.161, and 2.146 A˚ (u ¼ P O, OH). Two H sheets and the central O sheet form the HOH block, and adjacent HOH blocks link via a common X D anion of two D octahedra. In the I (Intermediate) block between adjacent HOH blocks, there are two interstitial cation sites, A and B, and [13] [6] a WA site, partly occupied by H2O. The A site splits into two partly occupied sites, A(1) and A(2), with A(1)–A(2) ¼ 1.108 A˚ . The [13]A(1) site is occupied at 90.5%: mainly by K, with minor Sr and Cs, ,A(1)–u. ¼ 3.326 A˚ ; the [6]A(2) site is occupied ˚ at 7.5% by Na: [A1.85Na0.15], ,A(2)–u. ¼ 2.29 A (u ¼ O, F, H2O). The aggregate content of the A site is (K1.78Sr0.02Cs0.01 [10] ˚ Na0.15A0.04)R2, ideally K2 apfu. The B site is occupied by (Na0.88Ca0.12), ,B–u. ¼ 2.646 A. The WA site is occupied at 7.5% by H2O: [A1.85(H2O)0.15] pfu. The presence of OH and H2O groups in the laverovite structure was confirmed by infrared spectroscopy. The mineral is named ‘‘laverovite’’ after Professor Nikolay Pavlovich Laverov (1930–2016), Academician of the Russian Academy of Sciences, a prominent Russian ore geologist and an expert in uranium ore deposits and radiogenic waste 2þ disposal. Laverovite is a Mn-analogue of zircophyllite, K2NaFe 7Zr2(Si4O12)2O2(OH)4F. Keywords: laverovite, new mineral, astrophyllite supergroup, Mont Saint-Hilaire, Quebec,´ electron microprobe analysis, crystal structure, FTIR spectroscopy. § Corresponding author e-mail address: [email protected] Downloaded from https://pubs.geoscienceworld.org/canmin/article-pdf/57/2/201/4669009/i1499-1276-57-2-201.pdf by Elena Sokolova on 27 March 2019 202 THE CANADIAN MINERALOGIST INTRODUCTION 14 minerals of the astrophyllite supergroup are divided into three groups based on (1) the type of self-linkage Laverovite, ideally K2NaMn7Zr2(Si4O12)2O2 of HOH blocks, i.e., (a) HOH blocks link directly via P (OH)4F, is a new kupletskite-group (astrophyllite D–X D–D bridges, or (b) HOH blocks do not link supergroup, IMA 2017D, Sokolova et al. 2017a) directly; and (2) the dominant cation of the O sheet mineral. It was found in the sample R060216, which [the C group: C7 apfu (atoms per formula unit)]. In the P is the property of the RRUFF Database, University of astrophyllite group, HOH blocks connect via D–X D– 2þ Arizona, Tucson, U.S.A. The sample is from the D bridges, Fe is dominant at C7; in the kupletskite P Desourdy quarry which later became part of the Demix group, HOH blocks connect via D–X D–D bridges, 2þ quarry which in turn was subsumed by the Poudrette Mn is dominant at C7; in the devitoite group, HOH P quarry, Mont Saint-Hilaire, La Vallee-du-Richelieu´ blocks do not connect via D–X D–D bridges. RCM, Monter´ egie,´ Quebec,´ Canada. The mineral is The general formula for the astrophyllite-super- named ‘‘laverovite’’ (pronunciation: la-’v e r-o-vaIt; group minerals is of the form A2pBrC7D2(T4O12)2 O O P Russian-Cyrillic: macgrpcjt) after Professor Nikolay IX D2X A4X DnWA2, where C [cations at the M(1–4) Pavlovich Laverov (Cyrillic: Ojlpmak Qacmpcjy sites in the O sheet] ¼ Fe2þ, Mn, Na, Mg, Zn, Fe3þ, Ca, Macgrpc) (1930–2016), Academician of the Russian Zr, Li; D (cations in the H sheets) ¼ [6,5]Ti, Nb, Zr, Academy of Sciences, a prominent Russian ore Sn4þ, [5]Fe3þ, Mg, Al; T ¼ Si, minor Al; the I geologist and an expert in uranium ore deposits and (Intermediate) block is composed of the peripheral radiogenic waste disposal. Professor Laverov was a layers of the form A2pBrWA2 where p ¼ 1,2; r ¼ 1,2; A 2þ great scientist who had major impact both on the ¼ K, Cs, Ba, H2O, Li, Rb, Pb , Na, A;B¼ Na, Ca, principal areas of his work and on the organization of Ba, H2O (only in sveinbergeite), A;WA ¼ H2O, A, and science in Russia. Professor Laverov was President of I represents the composition of the central part of the I O O the Academy of Sciences of the Kyrgyz SSR (1987– block, e.g., (PO4)2(CO3) in devitoite; X D ¼ O; X A ¼ P A 1988) and Vice-President of the Russian Academy of OH, F; X D ¼ F, O, OH, H2O, , where n ¼ 0, 1, 2 for P Sciences (1991–2013); he was also Director of the (X D)n. The A site can split into A(1) and A(2) sites. Institute of Geology of Ore Deposits, Petrography, Table 1 lists ideal structural formulae for the 14 Mineralogy and Geochemistry of the Russian Acade- astrophyllite-supergroup minerals. my of Sciences (IGEM RAS) (1991–2003). The new mineral species and its name were approved by the OCCURRENCE AND MINERAL ASSOCIATION Commission on New Minerals, Nomenclature and The laverovite studied in this work is a part of Classification, International Mineralogical Association sample R060216, which is the property of the RRUFF (IMA 2017–009b). The holotype specimen of lavero- Database, University of Arizona, Tucson, U.S.A. vite has been deposited in the collections of Royal Sample R060216 came from the Royal Ontario Ontario Museum, Toronto, Ontario, Canada; ROM Museum (ROM accession number M26526), Toronto, accession number is M57542. Here we report the Canada. The sample is from the Desourdy quarry description and crystal structure of laverovite, a new which later became part of the Demix quarry which in mineral. turn was subsumed by the Poudrette quarry, Mont Saint-Hilaire, La Vallee-du-Richelieu´ RCM, Mon- THE ASTROPHYLLITE SUPERGROUP ter´ egie,´ Quebec,´ Canada. Associated minerals are Here we give general information on the astro- zircophyllite, kupletskite, astrophyllite, aegirine, anal- phyllite supergroup (Sokolova et al. 2017a), so that the cime, orthoclase, and albite. Laverovite formed as a site nomenclature and details of the structure are late-stage hydrothermal mineral in a nepheline-syenite pegmatite. explained prior to their use in the sections on chemical In sample R060216, astrophyllite-supergroup min- analysis and structure refinement. The astrophyllite erals occur as transparent pale-brown to dark-brown supergroup is divided into three groups: the astrophyl- elongated lath-like crystals. Each grain of sample lite group, the kupletskite group, and the devitoite R060216 is an intergrowth of four minerals: lavero- group (Table 1).
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