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EVOLUTION of Nb,TA.OXIDE MINERALS in the PRAS

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EVOLUTION of Nb,TA.OXIDE MINERALS in the PRAS 535 The Carndian M ineralo g ist Vol.36, pp. 535-545 (1998) EVOLUTION OF Nb,TA.OXIDEMINERALS IN THE PRAS|VA GRANITICPEGMATITES, SLOVAKIA. II. EXTERNALHYDROTHERMAL Pb,Sb OVERPRINT PAVELUHERI,PETR dBMff ANDRON CHAPMAN Department of Geological Sciences, University of Manitoba, Wnnipeg, Manitoba R3T 2N2 JOZF;FHAIAR Geological Survey of Slovak Republic, Mlynskd dolitta l, 817 04 Bratislava, Slovak Republic OTOMIKO Slovak National Museum. Vaiansk€hondbrelie 2. 81I 02 Bratislava. Slovak Reoublic ABSTRACT Titanite, fersmite, pyrochlore-group minerals and rom6ite in two small dikes of relatively poorly fractionated pegmatite, located in the parent Hercynian Pra5ivd biotite granodiorite-granite, in cenfial Slovakia, were generated by hydrothermal alteration ofprimary columbite, titanian ixiolite and niobian-tantalian rutile. The early titanite has elevated contents ofNb, Ta, Al and Fe, and the fersmite is very REE-poor. Pyrochlore, microlite, betafite, uranpyrochlore, uranmicrolite, stibiomicrolite, stibiobetafite,plumbomicrolite and severaltransitional compositions were identified in the next generation,most ofthem Si-bearing. The late romdite is considerably enriched in M, Ta, U and Si. The hydrothermal fluids mobilized Nb, Ta" 11, U, Fe, Si, and probably also Ca and Na from the primary minerals of the pegmatite, but Sb and Pb must have been imported from an external source.The hydrothermal overprint is attributed to the samemetamorphic - magmatic solutions that causedthe nearby Sb + Au and Pb-Zn-Sb sulfide deposits. Keywords: titanite, fersmite, pyrochlore, microlite, betafite, uranpyrochlore, uranmicrolite, stibiomicrolite, stibiobetafite, plumbomicrolite, rom6ite, granitic pegmatite, Pra5iv6, Slovakia. Sopnuarns L'assemblagede titanite, fersmite, min6raux du groupe du pyrochlore et rom6ite dans deux petits filons de pegmatite granitique peu 6volu6e,li6s au pluton granitique et granodioritique hercynien de Pra5ivd,en Slovaquie centrale,r6sulte de I'alt6ration hydrothermale de la columbite, I'ixiolite titaniftre et le rutile niobifdre et tantalifbre primaires. La titanite pr6coce possddedes teneurs 6lev6esen Nb, Ta, Al et Fe, et la fersmite contient trbs peu de terres rares. Nous avons identifi6 pyrochlore, microlite, betafite, uranpyrochlore, uranmicrolite, stibiomicrolite, stibiobdtafite, plumbomicrolite, et plusieurs compositions transitionnelles dans la seconde g6n6ration de min6raux, dans la plupart des cas avec une teneur mesurable de Si. La rom6ite tardive est consid6rablement enrichie en Nb, Ta, U et Si. La phase fluide hydrotherrnale responsablede ces transformations a mobilis6 le Nb, Ta, Ti, U, Fe, Si, et probablement aussi le Ca et Na tr panie des min6raux primaires de la pegmatite, mais dans le cas de Sb et Pb, la source a d0 6tre externe h la pegmatite. La modification hydrothermale aurait 6t6 effectu6e par les m€mes infiltrations de fluide m6tamorphiqueet magmatiqueque celles qui sont I I'origine des gisementsavoisinants de sulfuresde Sb + 6u et Pb-Zn-Sb. (Traduit par la R6daction) Mots-clds: titanite, fersmite, pyrochlore, microlite, b6tafite, uranpyrochlore, uranmicrolite, stibiomicrolite, stibiob6tafite, plumbomicrolite, rom6ite, pegmatite glanitique, Pra5iv6, Slovaquie. IvrRopucuoN contain scarce Ti,M,Ta-minerals. The geological conditions and mineralogical characterization of both Two narrow (-<15 cm thick), homogeneous and S2A and S2B pegmatite dikes, as well as their primary generally primitive granite-pegmatite veins in the Nb,Ta-rich oxide minerals and products of their Sopotnica Valley, Pra5iv6 massif, central Slovakia exsolution (ferrocolumbite, manganocolumbite,titanian I Permanent address:Geological Institute, Slovak Academy of Sciences, Drjbravskd cesta 9, SK-842 26 Bratislava, Slovakia. E-mail address : [email protected] Downloaded from http://pubs.geoscienceworld.org/canmin/article-pdf/36/2/535/3447164/535.pdf by guest on 28 September 2021 536 THE CANADIAN MINERALOGIST ixiolite, Nb,Ta-rich rutile, armalcolite and ilmenite) Minerals of the pyrochlore group are the most were decribedin the companionpaper (Uher et al. 1998). widespread and the most diversified among the In this paper, we charactenze the secondary secondaryNb,Ta-minerals in both pegmatite bodies hydrothermal assemblageof the Pra5iv6 S2A and S2B studied. They replace mainly ferrocolumbite, rarely pegmatites. Besides fersmite, M,Ta-rich titanite and a titanian ixiolite, Nb,Ta-rich rutile, as well as titanite rather unusual Nb,Ta,U,Si-rich rom6ite, a surprisingly and fersmite, and appear as irregular microscopic broad spectrum of pyrochlore-group minerals was veinlets, fissure fillings and along boundary zones identified here, including U,Pb and Sb-bearingmembers. (Figs. l, 2). All recognizedspecies and compositional We also argue that the secondary assemblagewas varieties of this mineral group described below generatedby hydrothermal fluids from an external, 1.e., crystallized virtually simultaneously. For example, non-pegmatitesource. titanian ixiolite in grain #12 from the S2B pegmatite is replaced by Sb,U-rich pyrochlore to microlite, Expgnruenrar METHoDS uranmicrolite, nearly pure end-member microlite, sribiobetafite and stibiomicrolite (Fig. 2D). No The experimental methods are the same as those in systematic age relationshipcan be discerned among Uher et al. (1998); however,some of the conditionsof these phases,and $owth features of individual grains, electron-microprobeanalysis differ in detail. A Cameca compositionallyheterogeneous at the 1-100 pm scale, SX-50 electron microprobe at the Department of do not provide clues for the direction of compositional Geological Sciences,University of Manitoba was used. change with time. The same analytical conditions and standardswere Niobian-tantalian rombite was recognized in only used for fersmite as for the primary M,Ta-minerals. a single case, as a late fracture filling of primary The pyrochlore-group minerals and romdite were uraninite but younger than adjacent crystals of betafite analyzedusing an acceleratingpotential of 15 kV, beam (Fig. 3). This relationshipclassifies rom6ite as one of current 20 kV (Nb, Ta, Si, Ti, U, Sb, Fe, Mn, Ca, Pb, the last secondary minerals to form, and probably the Na, F) or 40 kV (Sn, Zr,Y, As, Bi, Sr, Ba, K, Cs), latest. counting time 20 s, beam diameter l-2 pm. The following standards were used: MnNbrOu (for NbLa, Chemical composition MnKa), mangan otantalite (TaM a), diopside (SiKa), TiO, (Ti Ka), SnO, (SnZa), ZrO, (Zr La), U O, (U M P), Titanite contains appreciable Nb, Ta, Al and Fe YAG (YLcr), mimetite (Aslcr), stibiorantalire (SbZcr), (presumedtrivalent). Predictably, the atomic sum of BiTaOo @rMp), microlite (NaKo, FKa), orthoclase ttrcse elements closely matches the deficit of Ti in all (KKcr), and pollucite (CsZc). For titanite, additional compositions (Table l). The dominant mechanismof elements were calibrated with zircon (SiKa) and subsdrudon (Al,Fe)3*(M,Ta)s+Ti++2 Gig. a) is accom- kyanite (AlKa) standardsat 15 kY 20 nA and 20 s panied in most casesby (Al,Fe)3*(F,C1,OHlGi4.O, ) ,. counting time. The overlap correction and PAP routine If real, this would be a novel substitution in addition to programsof Pouchou& Pichoir (1985) were applied. thoselisted by Bernau&Franz (1987) and eem! et at. (1995).A number of compositionsin addition to those Nb,Ta-Beannqc MTNERALs representedin Table 1 show an excessof cations at both the Ti and Si sites, combined with deficiency in the Ca Para g enetic relat ionshi p s site, if recalculated on either five anions or three cations; the Ca defrciency increaseswith normalization The textural relationshipsclearly show that all of on a total of 2 Ti + Si sites. This strongly suggests the pyrochlore-group minerals studied, as well as partial leaching of Ca from this earliest member of titanite, fersmite and rom6ite, replaced primary the secondary assemblageduring hydrothermal events columbite, titanian ixiolite and, locally, Nb"Ta-rich subsequentto the crystallization of titanite. rutile and uraninite. This replacement occurred along In the pegmatite samples studied, the fersmite is fractures, contacts and rims of the primary phases a Ca-rich, rare-earth-element-poor variety, with <0.5 (Fie. I to 3). wt.%oY2O3 $able 1). The Ti content can be relatively N io b i an-t an tal ian tit ani t e andfe rsmit e belon g to high, up to 0.26 atoms per formula unit, but negligible the earliest of the secondaryminerals. Titanite replaces in other cases.Excess of cations in the Ca site, very niobian rutile and ferrocolumbite, and is in turn cofilmon in other occirrences and so far unexplained,is replaced by plumbomicrolite (Fig. l). Fersmite exten- not in evidence at Pra5iv6. sively replaces ferrocolumbite beginning at the outer Minerals of the pyrochlore group A, -B2X6Y'. - surface of the grains, or forms complete pseudomorphs pHrO,whereX O2-,F-, OH- and Y= OH , F*, Oz-, are after a primary M,Ta-mineral, probably columbite or very diversified in terms of both A and B cations, as ixiolite (Figs. 2A, B). It rarely occurs as discrete(ca. illustrated by representativecompositions in Table 2. 10 pm) grains in M,Ta-rich rutile and is itself replaced In terms of mineral species, eight members were by stiboanmicrolite (Fig. 2B). identified: pyrochlore,microlite, betafite,uranpyrochlore, Downloaded from http://pubs.geoscienceworld.org/canmin/article-pdf/36/2/535/3447164/535.pdf by guest on 28 September 2021 Nb. TA-OXIDE MINERAIS. PRASTVA GRANITIC PEGMATTTES 537 Ftc. 1. Replacement of niobian rutile (r) by quartz (q), niobian-tantalian
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