In Partial Fulfil]Ment of the Requirements for the Degree of Master of Science
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CRYSTALLOGRÄ,PHY AND CHEMISTRY OF Li-Rb-Cs BEARTNG MTCAS FROM THE TANCO (CHEMALLOY) PEGMATITE, BERNIC LAKE¡ MANITOBA A Thesis Presented to The Faculty of Graduate Studies TTn i r¡crs ì l-r¡ Of ManitOba In Partial Fulfil]ment of the Requirements for the Degree of Master of Science by Romano Rinaldi October, i-970 ìì'iì-** 'j,, r t' i¡ ,.;;ì ¡ TABLE OF CONTENTS Þ.arr o LIST OF vi ABSTRACT vii CHAPTER T- INTRODUCTION General Geology and .l4ineralogy of the Tanco Pegmatite, Bernic Lake, nr^-.: !^1^^ I".I.CTJ.II L(JIJCT I B. The Present Stud.y 3 Previous !üork on Lithium-micas = D" Experimental Work Carried Out in the Present Study ñ Acknowledgements CHAPTER II DESCRIPTION OF TilE SPECÏMENS A. Specimens from the Tanco Mine, Bernic Lake .co.b Specimens from Other than Bernic Lake 11 CHAPTER TIÏ X-RAY DIFFRACTION STUDY A Powder Photographs" 13 P. Diffractograms L4 l. Structure Types 16 2" CelI Dimensions I9 Single Crystal Precession Investi- (l-^I.i^* Ct LJ\JJI ¿¿ I. Sample Preparation and Optic Orientation.. 22 2" Precession Photographs and Their Interpretation 24 l- l- l- Paqe CHAPTER TV CHEMISTRY A. l4ethods 3 3 B" Result,s 34 CHAPTER V OPTICS 37 CHAPTER VI DISCUSSION AND COMPARISON OF TEIE RESULTS A. Chemical Composition and Structure Type 43 U. The CelI Dimensions and the Chemical Composition with Special Reference to the Li^O,z¿¿ Rb^O and Cs.O Contents" " 46 C" The Variation of the Refractive fndices in Relation to the Contents of LirO, Rb^O¿¿ and Cs^o.." .""""""" 57 ]-V LIST OF TABLES Table Page 1" X-ray powder diffractometer data 18 2" Cell- d.imensions from the powder diffractograms 20 3 " Cell parameters obtained from precession photographs compared with the ones obtained with 'the powder method. " . 32 4 " Chemical analyses 35 5. Comparative refractive indices for muscovite and lepidolite (Deer et aI., 1966) .. ". 40 6" Optical study: Results.. 42 LIST OF FIGURES Figure Page 'l Location map of specimens in the Tanco Mine, Bernic Lake, Manitoba. L2 ¿- X-ray powder photographs" 1s X-ray powder d.iffractograms L7 Sample R.9 precession photographs 26 q Sample REN"1 precession photographs. 27 6" Sample REN"l precession photograph. " 2B '1 Samp1e REN.l cone-axis Picture 29 a Optical orientations of muscovite and lepid.olite" . Jð q Schematic representation of the relationship between Lj--O content and structure type 45 ¿ Ã7 IUAa Plot of Rb.O,¿'¿ wt"% against LirO, \üt.8... Plot of Cs.O,z¿ wt"% against LirO, wt.Z.. " o.. à.. 4B -L-LCI . The cell dimensions a ptotted against the Rb2O 50 contents i-n wt .Z " . " The ce1l dimensions b plotted against the Rb2O 51 contents in wt "Z " " " 12" Plot of the cell dimensions a against b 53 54 13" Plot of ceIl vofume against wt"% RbrO+CstO" ". " 1A Plot of the ß angle against Lí2O percent 56 l-5a wt.% against the refractive indices 5B " Plot of Li.O¿ l^' Rb.o wt"? against the refractive indices 59 Plot of ¿ Plot of CsrO wt"? against the refractive indices OU vl- ABSTRACT Twelve Li-Rb-cs-rich micas from the TANCO pegmatite, Bernic Lake, Manitoba and two from other localities, have been examined in detail by x-ray diffraction, optical and chemical methods. The x-ray study revealed the presence in three of the specimens of the structure type lM together with the 2MLt one is entirely lM, and. all the others are 2M, only. X-ray powder reftections that distinguish the two structure types are described. The following corre- lation between structure type and chemical composition was observed: micas witrl the 2Mr structure \^7ere found to contain up to 3-42 wt-% Li2O; from 3'5% to 4'282 LL'O bothstructuretypesappearwithprogressivelygreater amount of ].M; and above about 4.52 LLzo IM alone is likely to occur. The contents of Rb2o (up to 5"1- wt"%) and Csro (upto0.8wt.?)increaseroughlywithanincreaseinL] rOr but they do not seem to affect the change .in structure becausetwoofthespecimenswithhighestRb+Cshavethe 2Mt structure, and the lM type was found. in micas containing lower Rb + Cs but higher Li percentages " Li ' Rb and Cs have a rittle influence on the unit cell- dimensions ' gen- erally increasing the a and b dimensions and cell volume, and decreasing ß with increasing amounts. The variation vj-i of the two refractive indices in the plane of the cleavage' d.erived by the immersion method Ín monochromatic (tita) light, showed them to decrease with increasing LirO. The 2tt micas d.isplay the highest indices (y = L"599 - I"573), the lM types show the lowest values (yt = 1.566 - 1"561)" All the X-ray chemical and optical data indicate that the 2*L micas from the TANCO pegmatite belong to muscovite and lithian muscovite, and that the 1I{ structure type rs characteristic of lepidolite at this loca1ity. VAI]- CHAPTER I INTRODUCTION A. General Geology and lviineralogy of the Tanco Pegmatite, .Bernic Lake, Manitoba The Tanco pegmatite at Bernic Lake is located about 125 miles northeast of Winnipeg in the Lac du Bonnet l4ining Division of southeastern Manitoba" Previous works on the same pegmatite may refer to it as the Montgary or Chemalloy pegmatite, according to the names of the com- panies that in different times were mining the cleposit. At present the property is owned by Tanco" It is a complex zoned pegmatiLe which contains the western world's largest knov¡n reserve of pollucite, the chief ore mineraf of cesium, besides several lithium- bearing units. Other minerals of economic importance are Ta oxides, spodumene and beryl, the first ones being the main ore minerals presently extracted. The pegmatite is located near the margin of a granitic intrusive rock, and it. is bordered by amphibolite; the earl-ier rocl<s in the area and the pegmatite itsel-f are all of Precambrian age" The pegmatite body has an explored tengt,h along the major (east-west) axis of about 2t700 feet, the known length of the minor (north-south) axis being about l-,600 feet; the body varies in thickness from about 60 to about 210 feet and it is gently d.ipping (t15o) northwards. It consists of complex zones, each of which has a more or less distinctive mineral assemblage" The mineralogy (uickel, 196la) is typical of that of cesium-lithium deposits found in various parts of the world, the principal minerals being z quartz, a1kali and plagio- clase feldspars, lithium micas, spodumene, pollucite, and amblygonite-montebrasite; accessory minerals incl-ude beryl, lithiophilite, apatite, tourmaline, wodginite-tantalite- pseudoixiolite, tapiolite, cassiterite, microlite, ilmenite, rhodochrosite and some sulphides " The pegmatite is divided into six zones of primary crystallization and three replacement units by Wright (1963). According to ðernf (personal communication , Lgl0) Wright's division appears to be correct from the descriptive viewpoint; more emphasi-s on important accessory minerals should be shown in the names of zones, and metasomatic character of aplitic al-bite and pollucite is rather doubtful " WrÍght's zones: Cernf's zones : l" quartz-albite border t. quarÈz-albite border zone zorle 2 " perthite-quartz-plagio- 2. perthite-guartz-plagio- clase-muscovite walI zone clase-muscovite wall- zane Vüriqht' s zones : ðernf's zones: 3 " spodumene-perthite-plagio- 3 " spodumene-perthite-Plagio- c I ¡ qo-crrtv\aggùL arf.z intermediate clas e- amblygonite-quart z- ZVILE intermediate zone 4. spodumene-quartz inter- 4 " spodumene-amblygonite-quartz qt/r! h'i to con1- omnn¡- mediate zone with mi-nor \lenl i tiu¿v r: a'l vv¡¡ Çe¡lrlrv nartlr i {-a aneous ) 5 " microcline-quartz-inter- 5. microcline-quartz-berYl- mediate zone rnzndcrivvvsY ni f e intermediate zone q 6" quarLz core â \agqÀ94¡ttar|, õa\t'ê / ñ^ | 111^1tô t. }/v¿¿ I aplitic albite I lâñ1d^lrtê II lepidolite (replacing microcline of zone 5) rt_t_ porruclEe B" The Present Study The chemical and phvsical futl- definition of the micas from Bernic Lake was one of two objectives of Lhe present study, and the variation of the physical properties and crystal structure with the chemistry, especially with respect to the Li, Rb and Cs contents, \^7as the other objective. The present work is part of a broader project of investigation in the Mineral-ogical Laboratory of the University of Manitoba, of the minerals from the Tanco pegmatite which includes: wodginite-tantalite-pseudoixiol-ite by J.D. Grice and ambl-ygonite-montebrasite by Ivanka ðerná, carried out as M.Sc. thesis projects as wel-l" Other studies on the alkali feldspar, spodumene, petalite and other minerals from the d=ñ^ nnam={-.i {-a ÐOIttç IJçVlttCr (-I (.È q!:ra e UçI¡IYl-rai nn vaMçur-¡rr.i oä vqnrrl- L vJ}rrz fÞ . Vç!îarn(t ¡¡J , Þnqt-! vÐ L d.octoral- Fe]low. All studies should l-ead to a better understanding of the paragenesis of tl:e different minerals in the pegmatite. C" Previous Work on Lithium-Ùlicas 7\ h .i nrr rrrr¡,vrltant-^^- study on Li-micas and the relationship between polymorphism and composition in the muscovite-lepi- dol-ite series, was carried ouL by Levinson (1953). This study pointed out that the Li content is chiefly respon- sible for the change from a normal muscovite structure (2M.,)-J--¿ which tolerates up to about 3.3% of Li''O, to a "transitional structure" from about 3.4e" 4.0e" Li?O, and f inalIy to lepidolite with more than about 4.02 ri)o. In Levinson's work lepidolites with 4"02 5.12 LizO would l-ra 4Lt2t)wt r"zharaag thOse \^/ith more than 5 I % Li^O WOUId " ¿ be 1¡4 " A review of more than 100 analyses of Li-micas from the literature by M"D.