Canadian Mineralogist Vol. 18, pp. 25-29 (1980)

SABINAITE, A NEW ANHYDROUS -BEARING FROM MONTREAL ISLAND, QUEBEC

J.L. JAMBOR CANMET, 55S Booth Street, Ottawa, Ontario K1A 0G1

B.D. STURMAN Department of Mineralogy and Geology, Royal Ontario Museum, Toronto, Ontario M5S 2C6

G.C. WEATHERLY Department of Metallurgy and Materials Science, University of Toronto, Toronto, Ontario M5S 1A4

Abstract rant au maximum 0.01 x 0.001 mm. Biaxe negative, IV 85°. a 1.74(2), P 1.80(2), v 1.85(1), X presque Fine-grained, white, powdery coatings and chalky perpendiculaire aux plaquettcs. L'analyse donnc aggregates of sabinaite occur in vugs in a dawsonite- Na.O 20.7, CaO 0.2, ZrO, 39.1, HfO, 0.47, TiO, rich silicocarbonatite sill at Montreal Island, Que 12.0, CO, 27.1, total 99.57 (poids). La sabinaite bec. The mineral is platy. roughly pseudohexagonal, est anhydre; sa teneur en fluor est ndgligeable; with maximum dimensions 0.01 x 0.001 mm, biaxial sa formule est (Na,Ca)».M(Zr,Hf)4.,0Ti,.MO».Ti> negative with IV 85°, a 1.74(2). P 1.80(2). r (CO,)„.,n soit, idealemenl. Na„Zr,+,Ti,09(CO,)„ x 1.85(1), X nearly normal to the plates. Analyses = 0.25. Elle ne reagit pas avec les acides froids, gave Na.O 20.7, CaO 0.2. ZrO, 39.1. HfO, 0.47. mais est soluble avec effervescence dans HCI chaud. TiO, 12.0, CO, 27.1, total 99.57 wt. %. Sabinaite La sabinaite est monoclinique; les dimensions de is anhydrous and has low or negligible F. The la mnille, obtenues en partie par diffraction elec- analytical formula is (Na,Ca)R.M(Zr,Hf)4.j»Ti,.M troniquc et en partie aux rayons X sur cliche 0,.,„(CO.,),.,o, theoretically NasZr^TiA^COa),, de poudre. sont: a 6.605(3), b 10.186(5). c 37.94 where x — 0.25. The mineral is unreactive in cold (5) A, P ~ 90". D„lc = 3.41 pour Z = 8 (for acids but is soluble with effervescence in warm mule analytique), Dm. 3.36. Les cinq raies les HCI. Sabinaite is monoclinic; cell dimensions, ob plus intenses du cliche' de poudre sont: 8.97(10) tained partly by electron diffraction and partly (012). 2.991(6)(036), 2.017(5)(240), 1.847(6), from the powder X-ray pattern, are a 6.605(3), 1.646(5). Le spectre infrarouge confirmc la pre b 10.186(5), c 37.94(5) A, P ~ 90°. D„„ is 3.41 sence de carbonate et l'absence de H,0 et d'OH. g/cms for Z = 8 (analytical formula), whereas Par ATD et ATG, on obtient une perte de poids £)„„ is 3.36 g/crn". Strongest lines of the powder de 28.1% et surtout du ZrO, monoclinique commc pattern are 8.97(10)(012), 2.991(6)(036), 2.017 produit de decomposition. La nouvelle espece est (5X240). 1.847(6). 1.646(5). The infrared spec dcdiee a Ann Phyllis Sabina, de la Commission trum of sabinaite confirms the presence of car gcologique du Canada. bonate and the absence of H,0 and OH. DTA and (Traduit par la Redaction) TGA gave a weight loss of 28.1%. with decom position mainly to monoclinic ZrO,. Sabinaite is Mots-cits: sabinaite, silicocarbonatite, carrierc St- named in honor of Ann Phyllis Sabina, of the Michcl, Montreal, dawsonite, carbonate anhydre de Geological Survey of Canada. zirconium et de . Keywords: sabinaite, silicocarbonatite, St-Michel quarry, Montreal, dawsonite, anhydrous carbonate Introduction of zirconium and titanium. Dawsonite-bearing silicocarbonatite sills ex Sommaire posed in a limestone quarry at St-Michel, Mont real Island, Quebec, contain a varied mineralogy On trouve la sabinaite en enduits blancs, fine- ments grenus, pulvcrulcnts et en agrlgats crayeux that includes several unique barium- and zir dans les vacuoles d'un sill de silicocarbonatite a conium-bearing carbonates and a few as-yet- dawsonite sur l'ile de Montreal (Quebec). Elle unidentified minerals (Sabina 1979). In 1967 se prcsente en plaquettcs pseudo-hexagonales mesu- a new Na-Zr-Ti mineral was recognized and

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subsequently designated as mineral No. 5 (Sabi Compact aggregates have a vitreous lustre, but na 1976, 1979) For almost a decade only a in some cases flakes are aligned and impart a minute amount of this mineral was available, silky lustre to thin coatings. The hardness of but persistent collecting and X-ray identifi the mineral could not be determined. cations by A.P. Sabina eventually resulted in Optical and scanning electron microscopy of the acquisition of sufficient material for a sabinaite shows that it is platy and commonly chemical analysis and characterization. The new roughly pseudohexagonal. Grains are generally mineral is named sabinaite in honor of Ann equant, but most of the prism edges are ir Phyllis Stenson (n6e Sabina), whose initial work regular. A few grains are well formed (Fig. 1) led to the recognition of the unusual mineral and have crystal edges that intersect at 115 to assemblage at the St-Michel quarry, and whose 120°, thus accounting for the pseudohex perseverance in collecting and identifying these agonal crystal shape. Perfect basal cleavage is rare minerals has provided the main impetus evident from the persistent flaky habit of toward their study. The new mineral and name ground samples; a good cleavage normal to have been approved by the Commission on the base is visible in some SEM photographs. New Minerals and Mineral Names, I.M.A. Sabinaite is optically transparent and color Cotype specimens of sabinaite are in the Na less, biaxial negative with 2V (universal stage) tional Mineral Collection at the Geological Sur 85(5)°, a 1-74(2), 0 1.80(2), y 1.85(1). X is vey of Canada, Ottawa (61017 to 61024 in perpendicular (or nearly) to the plates. clusive), and in the Royal Ontario Museum, Sabinaite does not fluoresce in ultraviolet Toronto (M35902). radiation. However, in some specimens this inertness is obscured by the presence of films of a gibbsitc-typc mineral (No. 3 of Sabina Properties 1976, 1979) that has an intense, while fluo Physical and optical properties rescence under long-wave ultraviolet light. Sabi naite shows no reaction in dilute and concen Sabinaite occurs in silicocarbonatite in the trated (1:1) hydrochloric acid at room temper upper levels of the quarry, where it forms ature, but is readily soluble with effervescence white, powdery coatings and compact, chalky in warm HCI. Pycnometer measurement of an aggregates in vugs. The mineral is microscopi approximately 300-mg sample used for the chem cally flaky, with maximum dimensions of about ical analysis of sabinaite gave a density of 0.01 mm in width and 0.001 mm in thickness. 3.36 g/cm'.

X-ray data Sabinaite is too fine grained for standard single-crystal X-ray study. Electron-diffraction patterns of flat-lying plates show a net that can be interpreted as orthogonal, with h + k = In and dm = 10.2, dm, = 6.6 A. Observed forms for sabinaite therefore become {100} and {110}, platy {001}, with cleavages {001} and {100}. Attempts to obtain the third cell para meter by tilting the plates were not successful because of multiple diffraction and reciprocal lattice streaking. Controlled tilting experiments about [100] do not give identical patterns and indicate that the unit cell is not precisely ortho- rhombic. Therefore, either monoclinic or triclinic symmetry would be possible, but the systematic hkO extinctions indicate that the cell is mono clinic. The X-ray powder pattern of sabinaite was indexed by using the orthogonal dimensions from the electron-diffraction pattern and cal Fig. 1. SEM photograph showing the typical platy culating c and (j from the powder data. Satis habit and crystal shape (top right) of sabinaite. factory indexing was obtained with c = 37.94 Bar represents 1 p.m. A, $ = 90" (Table 1).

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TABLE 1. POWDER X-RAY DIFFRACTION DATA FOR SABINAITE by microprobe at CANMET, and Na,0, CO,

hM. hU and F were determined by wet-chemical methods 'est neas dealc W neas dcalc at the Geological Survey of Canada. No other 10 B.97 8.974 012 1 2.243 2.244 048 i S.10 5.093 020 1 2.153 2.150 0.2.16 elements were detected by microprobe. B 3.277 3.279 033 6 1.847 Tii.9a08.«(COs),.10, approximately Nao(Zr,Hf)4+» 2 3.252 3.254 202 2 1.824 1 3.009 3.010 131 3 1.795 Ti,Os(CO»)s assuming 33 O atoms and no F 6 2.991 2.991 036 8-8" ZrO? 39.4 38.8 39.1 39.27 Zr 4.174 ., MfO» 0.47 0.46 0.47 0.47 Hf 0.030 ' ,-*u DTA-TGA and Infrared Spectrum T102 12.2 11.8 12.0 12.05 Ti 1.976 1.98 C02 27.1 27.1 27.22 C 8.100 8.10 DTA and TGA curves of sabinaite were ob 0.6 <0.1 0.0 0 33.000 33.00 tained with a Mettler Thermoanalyzer at the §575799757 100.00 Royal Ontario Museum. A 6.8-mg sample heated JKlZh"1 8.848 from 430 to 470°C and 14.9% from 470 to

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558°C (cumulative 15.8%). In the second stage, (Bradley & Thornton 1973, Dervin et al. 1974). only 0.15% is lost from 811 to 895°C and The notable absence of absorption bands in 2.8% from 917 to 998 °C, but the reaction is the 3000-3900 and 900-1000 cm"* regions of incomplete. The product of heating to 998°C sabinaite (Fig. 2) confirms the absence of H,0 is monoclinic ZrO,. and OH in the mineral. A 7.3-mg sample of sabinaite run in a N, Because of the unusual composition of sabi atmosphere, at flow and heating rates as above, naite, the possibility that part of the carbon gave much more pronounced reactions and a might be structurally bound as oxalate was con similar two-stage loss: to 450°C the weight sidered. The first strong absorption band in loss is only 1.1%, but a major, sharp endo the infrared spectrum of sabinaite is centred thermic peak is centred at 519°C and the at about 1660 cm"'. The equivalent band in cumulative losses to 550 and 650°C are 18.8% oxalates is in the range 1600-1630 cm"1 and 20.3% respectively. The endothermic peak whereas carbonates generally have this band may signal the evolution of 6 CO,, correspond at lower wave-numbers. However, chemical anal ing to a calculated decrease in weight of 20.2%. ysis of sodium oxalate by the identical method Further CO, evolution is signaled by the oc used for sabinaite gave negligible CO,. More currence of a second endothermic peak between over, comparison of the infrared spectrum of 660 and 780°C and a 7.9% weight loss. Only sabinaite with spectra of carbonate compounds minor additional loss occurs between 780 and of zirconium (Kharitonov et al. 1967) shows that 900°C, and the cumulative total to 1010° is the absorption band at 1600 cm"' is vi (CO), 28.1%. The end product is monoclinic ZrO,, that at 1330 cm-' is v» (CO), and that at 1080 with faint traces of cubic ZrO, and Na,ZrO, cm"' is probably v, (CO). According to litera also evident on the X-ray pattern. A duplicate ture cited in Kharitonov et al. (1967), v (ZrO) run to 587°C was used to examine the product should appear as an intense, narrow absorption formed after the first-stage weight loss. The band between 800 and 1000 cm"1; such X-ray powder pattern obtained was that of a band appears in the spectrum of sabinaite at stabilized cubic ZrO, with a 5.05 A; Katz about 830 cm"'. The positions of the CO (1971) reported that pure cubic ZrO, has a absorption bands in sabinaite indicate that link cell edge of 5.09 A. age of zirconium and carbonato groups is most The infrared spectrum of sabinaite is shown likely bidentate or bridging rather than uni- in Figure 2. Sabinaite is a most unusual com dentate. pound in that no other anhydrous zirconium carbonates are known to occur either naturally Associated Minerals or in synthetic systems. Although normal car bonates of zirconium and hafnium have eluded Sabinaite is commonly present in the silico synthesis, several hydrated zirconium salts with in small amygdule-like pockets and basic carbonato anions have been isolated as coatings in cavities lined with calcite, daw-

MICRONS 2.5 6 10 15 20 30 50 1— <~n—n—n

4000 3(300 2000 CM Fio. 2. Infrared spectrum of sabinaite.

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sonite and quartz. The most persistent asso References ciate is a fluorine-bearing gibbsite-type mineral whose characterization has not been completed- Bradley, D.C. & Thornton, P. (1973): Zirconium Sabinaite coats all of the above minerals, as and hafnium. In Comprehensive Inorganic Chem well as weloganite and cryolite. Pyrite, galena, istry 3, 419-490. Pergamon, Oxford, England. pink barite, plates of ilmenorutile, and yellow Dervin, J. Faucherre, J. & Pruszek, H. (1974): ish ankerite and have been noted as Etude en solution et a l'etat solide des carbo inclusions in sabinaite. These observations in nates complexes de zirconium et d'hafnium. Rev. dicate that sabinaite was formed late in the Chimie Mineral. 11, 372-387. dcpositional sequence of the vug minerals. Dutrizac, J.E. (1978): A comparative analysis of Athabasca tar sand zircon and chemical analysis Films of blackish hydrocarbon have been ob of some other Canadian zirconium minerals. Dep. served as coatings on weloganite, quartz and Energy, Mines Res., CANMET Lab. Rep. MRP/ calcitc crystals; in one unusual case, sabinaite MSL 78-180 (TK). coats massive white dawsonite, pink garnet, Katz, G. (1971): X-ray diffraction powder pattern and grey quartz and calcite that occur in a pod of metastable cubic ZrO,. J. Amer. Ceramic Soc. containing graphite flakes. 54, 531. Kharitonov, Yu. Ya., Pospelova, L.A. & Zaiysev, Acknowledgements L.M. (1967): Infrared spectroscopic study of car- bonato-compounds of zirconium. Russ. J. Inorg. Material for this study was collected with the Cltem. 12, 1390-1395. kind permission of Francon, Division de Can- Mandarino, J.A. (1979): The Gladstone-Dale farge Limitee. Wet-chemical and microprobe relationship. III. Some general applications. Can. analyses were provided by J.-L. Bouvier of the Mineral. 17, 71-76. Analytical Chemistry Section and A.G. Plant Pyatenko, Yu. A. & Voronkov, A.A. (1978): of the Mineralogy Section, Geological Survey Comparative crystal-chemical functions of tita of Canada. Additional assistance was generously nium and zirconium in mineral structures. Int. given by A.C. Roberts of the Geological Survey Geol. Rev. 20, 1050-1058. of Canada, and by CANMET personnel E.E. Sabina, A.P. (1976): The Fracon [a-ic] quarry, a Laufer, E.J. Murray, J.H.G. Laflamme and the mineral locality. Geol. Surv. Can. Pap. 76-1B, late D.M. Farrell. DTA and TGA curves were 15-19. obtained at the Royal Ontario Museum through (1979): Minerals of the Francon quarry the courtesy of F.J. Wicks and R.A. Ramik. (Montreal Island): a progress report. Geol. The interest and invaluable help given by J.E. Suv. Can. Pap. 79-1A, 115-120. Dutrizac of CANMET are greatly appreciated. All of the sabinaite used in this study was collected and verified by A.P. Sabina prior Received May 1979, revised manuscript accepted to her knowledge of the naming of the mineral. August 1979.

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