manganocolumbite and cassiterite exsolution lamellae in ilmenite
Transcription
manganocolumbite and cassiterite exsolution lamellae in ilmenite
Hartmut Beurlen, al. Estudos Geológicos v. 16 (2):et3-15 MANGANOCOLUMBITE AND CASSITERITE EXSOLUTION LAMELLAE IN ILMENITE FROM THE PITOMBEIRAS PEGMATITE (ACARI – RIO GRANDE DO NORTE) IN THE BORBOREMA PEGMATITIC PROVINCE, NE-BRAZIL. Hartmut Beurlen*1 Rainer Thomas2 Marcelo R. Rodrigues da Silva3 Dailto Silva4 1 Programa de Pos-Graduação em Geociências, UFPE. * [email protected] 2 GeoForschungsZentrum Potsdam, Telegrafenberg B 120, D14473 Potsdam, Alemanha 3 Departamento de Geologia, UFPE. 4) Instituto de Geociências – UNICAMP. RESUMO: Lamelas de exsolução de manganocolumbita, de cassiterita e de hematita são observadas em cristais primários de ilmenita manganesífera, no pegmatito Pitombeiras 1, na Província Pegmatítica da Borborema, no município de Acari, Estado do Rio Grande do Norte, Brasil. O pegmatito hospedeiro é heterogêneo e tem como encaixante o granito porfirítico do batólito de Acari-Pau Pedra (580 Ma), por sua vez intrusivo nos biotitaxistos neoproterozóicos do Grupo Seridó. As exsoluções de hematita tem forma discoidal em seção prismática e arredondada a irregular amebóide em seção pinacoidal da ilmenita hospedeira, semelhante às numerosas ocorrências descritas na literatura. As exsoluções de cassiterita são raras, com formas discoidais de até 4 por 15 m, com orientação em três direções, fazendo 120° quando observadas na seção pinacoidal da ilmenita, relação similar à descrita para exsoluções de rutilo em ilmenita na literatura, supostamente orientadas segundo o romboedro II da mesma {hh2hl}. As exsoluções de ferrocolumbita são bem mais freqüentes, enriquecidas em titânio e escândio, e se apresentam com formas tabulares muito finas (usualmente menores que 2 de espessura e 30 de comprimento), dispostas muitas vezes em arranjos hexagonais, provavelmente orientadas segundo o romboedro III da ilmenita {213l}, já que fazem um ângulo de aproximadamente 80° com as lamelas de cassiterta. A composição da ilmenita hospedeira distingue-se por um conteúdo, em solução sólida, de 1,5 a 3,4 % peso de (Ta+Nb)2O5, e até 0,25 % peso de SnO2, indicando reduzida solubilidade em condições de baixa temperatura. Já a solubilidade a altas temperaturas pode ser estimada em 3,0 a 4,5 % peso de (Nb+Ta)2O5, com base na composição modal hóspede/hospedeiro. Palavras chave: exsoluções de manganocolumbita; cassiterita; ilmenita hospedeira; pegmatito granítico; química mineral; Província Pegmatítica da Borborema. Estudos Geológicos v. 16 (2), 2006 001 Estudos Geologicos Vol 16 - 2.p65 3 3 24/5/2007, 11:58 Manganocolumbite and cassiterite exsolution lamellae in ilmenite from the pitombeiras pagmatie... ABSTRACT: Exsolution lamellae of manganocolumbite, cassiterite and hematite are observed in primary manganoan ilmenite crystals from Pitombeiras Pegmatite, in Borborema Pegmatitic Province, Acarí County in the State of Rio Grande do Norte-NE-Brazil. The hosting heterogeneous pegmatite is intrusive in the porphyritic granite of the Acarí-Pau Pedra batholith (0.58Ga), which intruded Neoproterozoic biotite-schists of the Seridó Group. The hematite exsolutions are disc shaped in prismatic sections and rounded to irregular ameboid shaped in pinacoidal sections, oriented along the ilmenite pinacoid, as described from numerous other occurrences in the literature. The rare cassiterite exsolutions form small, disc shaped (up to 4 by 15 m) lamellae arranged in three directions with angles of 120°, when observed in a pinacoidal section of the hosting ilmenite. A similar relation is found in the literature for rutile exsolution lamellae in ilmenite, supposedly arranged along the rhombohedron II {hh2hl} of the host. The much more frequent ferrocolumbite exsolutions are very thin tabular shaped, usually less than 2 m thick and 30 m long, commonly forming hexagonal arrangements, supposedly oriented along the rhombohedron III {213l)} of the ilmenite (because of the 80° angle observed with the cassiterite lamellae. The composition of the hosting ilmenite is distinguished by a content of 1.5 to 3.4 wt.% (Ta+Nb)2O5, and less than 0.25 wt. % SnO2 in solid solution, indicating a low cassiterite and columbite group mineral solubility at room temperature. At higher temperatures, the solubility of 3.0 to 4.5 wt. % (Ta+Nb)2O5 and 0.4% cassiterite can be estimated, based on the modal relationship between the hosting ilmenite and the exsolution lamellae. Keywords: manganocolumbite exsolution lamellae; cassiterite; ilmenite host; mineral chemistry; granitic pegmatite; Borborema Pegamatitic Province. 4 001 Estudos Geologicos Vol 16 - 2.p65 Estudos Geológicos v. 16 (2), 2006 4 24/5/2007, 11:58 Hartmut Beurlen, et al. INTRODUCTION During the study of compositional variations in columbite group minerals in the Borborema Pegmatitic Province as possible tracers of the degree of fractionation of different pegmatite types (Beurlen et al. 2007), an unique occurrence of manganoan ilmenite with exsolution lamellae of titanian-scandian manganocolumbite, cassiterite and hematite was registered. The tabular ilmenite crystals were found as main component in heavy mineral concentrates from the Pitombeiras 1 pegmatite. The concentrate was provided by prospectors and, according to their information, collected in the Pitombeiras 1 pegmatite. Later, identical ilmenite crystals were found in blocks of quartz collected by the authors in the soil covering this pegmatite. The Pitombeiras 1 pegmatite may be reached leaving the main Road from Acarí to Caicó in the State of Rio Grande do Norte, 8.8 km southward from Acarí, following to WSW by a secondary unpaved road for 1.9 km. The pegmatite is one of a group of small pegmatites with nearly ESE strike and NNE dip, enclosed in the southern part of the Acarí-Pau Pedra batolith (APPB). The group includes the Canoa pegmatite, referred by Beurlen et al. (2004) as the first occurrence of "strüverite" in the BPP, located 1.9 km to SW from Pitombeiras 1. Crystals of "strüverite" (this mineral, a high tantalian rutile, was recently disabled by the IMA commission and should be considered as a high tantalian rutile with up to 45wt% Ta2O5) were now found also in the intermediate zone of the Pitombeiras 1 pegmatite, identical in form and composition to that one described from the Canoa pegmatite. As some of the exsolution bearing ilmenite crystals of the heavy mineral concentrate are partially included by strüverite crystals with the same composition and intergrowths, there is no doubt about the provenance of this ilmenite. The registration and descrip- tion of these manganocolumbite and cassiterite exsolutions seems to be of interest because no similar intergrowths were referred in the pertinent literature (e.g. Rolff 1946, Johnston Jr 1945, Ramdohr 1969, McLeod & Chamberlain 1969, Uytboogart, 1951, Antony et al. 1997, Uher et al. 1998, Cerný & Ercit 1989, Craig & Vaughan 1981, Ixer & Duller 1998) GEOLOGY The Canoa-Pitombeiras pegmatite swarm occurs approximately. 1.5 km westwards from the intrusive contact of the hosting APPB with cordierite-sillimanitegarnet-biotite schists of the Seridó Formation, top of the Neoproterozoic Serido Group (Van Schmus et al. 2003). This location is close to the western limit of the Borborema Pegmatitic Province (BPP) (Fig. 1). The APPB granitic facies in this area is characterized by proeminent white K-feldspar phenocrysts and fine to medium grained biotite rich matrix, studied in detail by Jardim de Sá et al. (1981, 1986). According to geochemical data, discussed by Jardim de Sá (1994) the calcalkaline to shoshonitic I type magma source of the APPB was generated by the melting of a cca. 2.0 Ga old granitic crust, with subordinated participation o juvenile (transition to A type) and/or metassedimentary rocks. U/Pb in zircon ages of 555 and 579 Ma were obtained for the APPB by Legrand et al. (1991) and Jardim de Sá (1994), respectively. These ages are much higher than the 480 to 533 Ma supposed for the pegmatites of the BPP (Ebert 1969, Almeida et al. 1970 and Araújo et al. 2001, Baumgartner et al. 2006). According to da Silva et al. (1995), Araújo et al. (2005) and Baumgartner et al. (2001) a more likely source of the pegmatites of the BPP are peraluminous pegmatitic granites, supposedly related to a late retrometamorphic stage associated with an extensional-transpressional tectonic event at 525 Ma (Araú- Estudos Geológicos v. 16 (2), 2006 001 Estudos Geologicos Vol 16 - 2.p65 5 5 24/5/2007, 11:58 Manganocolumbite and cassiterite exsolution lamellae in ilmenite from the pitombeiras pagmatie... jo et al. 2005). Baumgartner et al. (2006) found an age of 528 Ma (U/Pb in monazite) for one of these pegmatitic granites and considered it too high to corroborate this intrusions as source for the mineralized pegmatites (509 to 514 Ma, U/Pb in columbite group minerals). As in other pegmatites of the group enclosed in the APPB, in Pitombeira 1, a fast transition from a decimetric homogeneous steeply dipping pegmatite vein (80° NE) to metric to decametric, gently (30 o to 60o NE) dipping lenses, with very incipient zoned structure and subordinated discontinuous quartz cores, plunging to NW, is observed (Fig. 2), contrasting with the usually well zoned larger pegmatites of the Parelhas-Equador area. The poorly zoned part of the Pitombeiras pegmatite is formed by a medium to coarse- grained wall zone (1 to 5cm grain size), composed of quartz, K-feldspar and subordinated albite, with sporadic biotite plates growing perpendicular to the contact with the enclosing granite. Main accessory minerals are garnet, muscovite, beryl, and magnetite. The wall zone locally grades inwards into a blocky feldspar + milky quartz zone with individual K-feldspar crystals reaching up to 1.5m also oriented perpendicular to the contact, showing local replacement and overgrowths by albite. Discontinuous lenses of massive, milky quartz, locally with masses of rose quartz in the center (Fig. 2a). Black, saccharoidal tourmaline aggregates in thin veins crosscut the quartz core and blocky feldspar (Fig. 2b), or form decimetric, coarse grained, replacement pockets at the transition to the quartz core. Beryl crystals (usually 5 to 10 cm sized) are Figure 1 – Borborema Pegmatitic Province on a simplified geologic base adapted from Brasil (1998, 2002), with the location of the Pitombeira pegmatite (number 3) discussed in the text. 6 001 Estudos Geologicos Vol 16 - 2.p65 Estudos Geológicos v. 16 (2), 2006 6 24/5/2007, 11:58 Hartmut Beurlen, et al. sporadically observed in all zones. Beryl crystals with yellowish-green colors predominate in the wall zone, while blue colored, gem quality aquamarine may sometimes be observed in the transition between the blocky feldspar and quartz core. PETROGRAPHY The samples of columbite-cassiterite exsolution bearing ilmenite (type 1) were found first as the main component in heavy mineral concentrates provided by miners, together with some larger ferrocolumbite crystals. Some of the tabular ilmenite crystals (up to 8 mm large in composite grains of the concentrate) are in direct single planar contact with crystals of strüverite, indicating simultaneous growth. The strüverite by its turn contains inclusions of ixiolite (probable exsolution lamellae according to Beurlen et al. 2007) and cassiterite. Another sample of the same ilmenite type was found included in massive quartz blocks in the soil covering the Pitombeiras 1 pegmatite. No sample of this ilmenite was found in the pegmatite outcrops, but strüverite crystals with the same composition and intergrowths with ixiolite were found in blocks of typical pegmatitic mineral association of the intermediate zone in the dumps of this pegmatite and in the nearby Canoa pegmatite, already described in detail by Beurlen et al. (2004). In one of these pegmatite blocks a 5cm large strüverite crystal is in direct contact with a 5cm large beryl crystal, both idiomorfic against a large Kfeldspar crystal and massive milky quartz. The primary pegmatitic origin of both, the strüverite and this exsolution bearing ilmenite, is thus well established. Figure 2 a View of the western end of the Pitombeira 1 pegmatite. At the surface the pegmatite is homogeneous, less than 20cm thick, with a high dip of 8O° to north (right side of the foto), enclosed by a porphyritic granodiorite of the APPB. Towards the depth, a fast increase of the thickness to more than 6m, a decrease of the dip to 45°, and an incipient zoned structure is observed, formed by a 2 to 3m thick wall zone (W) with crystal size increasing towards the center and an up to 4m thick quartz core (Q) is observed (now almost completely extracted, see the hole were the man is seated). b Detail of the northern wall of the pegmatite excavation, with an incipient formation of intermediate zone (I) formed by meter sized K-feldspar crystals oriented normally to the contact, at the transition between the wall zone (upper part – W) and the quartz core (darker, lower part – Q). Estudos Geológicos v. 16 (2), 2006 001 Estudos Geologicos Vol 16 - 2.p65 7 7 24/5/2007, 11:58 Manganocolumbite and cassiterite exsolution lamellae in ilmenite from the pitombeiras pagmatie... A second type of ilmenite was described by Beurlen et al. (2004) as part of a late hydrothermal alteration product of the strüverite. This ilmenite 2 is always intergrown with microlite and/or pyrochlore and some niobian sphene, replacing the borders of strüverite crystals. This ilmenite 2 usually has a 30 to 60 mol% pyrophanite component – thus being actually a pyrophanite in some cases-, much higher than the Mn-content observed in the type 1 ilmenite (up to 10 mol%). In addition, in the type 2 ilmenite no exsolution bodies are found, also distinguishing this generation from type 1 ilmenite. The type 1 ilmenite contains three different exsolved phases. The first one is titanian hematite forming disc shaped lamellae, up to 10 m by 30 m large, oriented parallel to the pinacoid (0001), as can be seen in prismatic sections of the hosting ilmenite, and with a diameter of about 30 m and rounded to ameboidal shapes shown in the pinacoidal section. This type of exsolution bodies is the most common one observed in ilmenite in many different types of occurrences (Ramdohr 1969). The second phase that occurs as product of exsolution in this ilmenite type is cassiterite, in the form of rare, randomly distributed, disc shaped bodies, up to 4 m by 15 m large, oriented along three directions with angles of 120° when observed in pinacoidal sections of the ilmenite. In the literature similar crystallographic relations are described for rutile exsolutions, supposedly oriented along the rhombohedron II {hh2hl) of the hosting ilmenite according to Edwards (apud Ramdohr 1969). The third exsolved phase is a columbite-group mineral (or possibly ixiolite), which occurs as thin, tabular shaped (< 2 m by 30 m) exsolution bodies frequently forming hexagonal arrangements in a pinacoidal section of the hosting ilmenite and in two directions when seen in prismatic sections, in this case forming an angle of about 30 to 40° with the hematite lamellae. 8 001 Estudos Geologicos Vol 16 - 2.p65 These columbite lamellae are probably exsolved along the rhombohedron III {2hh3hl) of the hosting ilmenite, because they are oriented forming an angle of nearly 80° with those of the cassiterite lamellae. The definitive identification as ixiolite or columbite-group mineral in the present case is not possible. This is because the composition obtained by EMPA in a few lamellae larger than 2 m thick, and in a few even larger grains formed by collection recristallization from the exsolution lamellae, is very close to the upper limit of 10 wt% (TiO2+SnO2+ Sc2O3) content admitted for the, in this case disordered, columbite group phases (Wise et al. 1998). For all three of the exsolved phases, the very homogeneous size, shape and distribution in the hosting ilmenite, and the clearly established crystallographic host/ guest relationship for each phase are considered to assure its generation by a true exsolution process (Fig. 3). The modal proportion of the exsolution lamellae was estimated roughly to be of 7.5% hematite, 2.0% columbite and 0.2% cassiterite. This primary ilmenite type 1 and its exsolutions are locally replaced along fractures and grain borders by a myrmekitic intergrowth of titanian maghemite and niobian rutile, probably formed by supergene alteration. CHEMISTRY Analytical methods Semi quantitative chemical analyses of the samples for preliminary mineral identification and imaging were obtained by SEM at the University of Campinas São Paulo using a SEM Leo 430i, Cambridge, EDS mod. Cat. B, using the following working conditions: 20Kv, 30 seconds acquisition time, using the following standards: Tao (Ta Mα), Nbo (Nb Lα ), Sno(Sn Lα), Tio(Ti Kα), Vo (V Kα), Sbo (SbLα), Bio (Bi Mα) Zro (Zr Lα), Uo (UMα), Hf o (Hf Mα) PbF2 (PbMα), BCR2 (Fe Kα, Mn Kα, Al Kα, Ca Kα, Na Kα, Si Kα, K Kα). Estudos Geológicos v. 16 (2), 2006 8 24/5/2007, 11:58 Hartmut Beurlen, et al. Quantitative data were obtained by electron microprobe analyses (EMPA) at the GeoForschungsZentrum Potsdam-Germany, using Cameca SX 50 and SX 100 EMPA equipments at 20 kV and 40 nA, with acquisition times of 20 seconds for Fe Kα, Mn Kα, Ti Kα, Sc KαMg K , Al Kα, Ca Kα, NaKα, Si Kα, K Kα, 30 seconds for Nb, Lα, SnLα, Sb Lα, Zr LαHf Mα, Y Lα, Cs Lα, Ba Lα, and 50 seconds for Ta Lα, Bi Mα, U Mα, PbMα, ThMα, Ce Lα, La Lα, using the following standards: albite (Na), ilmenite (Fe, Ti), cassiterite, orthoclase (K,Al), titanite (Si,Ca,Ti,), zircon, Nbo, Tao, Tho, Uo, vanadinite, BaSO4, CePO4, LaPO4, YPO4, ScPO4, InSb, MgO, HfO2, MnTiO3, Bi2S3 , pollucite. The calculation procedure to obtain the cationic composition in atoms per formula unit (APFU) listed in Table 1, was to normalize them in a first step to a sum of 24 oxygen ions for most tantalates, to allow an easier comparison. In a second step, in cases where the obtained cation sum surpassed the corresponding theoretical value (12 cations for phases of the columbite, tapiolite, and ixiolite groups, and niobian rutile – strüverite, etc.), the Fe2+ content was partially converted to Fe3+ (according to Ercit et al. 1992c, 1992d) by trial and error until the cation sum reached the value of 12.000± 0.002 cations. In the case of wodginite group minerals the normalization was made recalculating Fe2+ to Fe3+ cations as much as necessary to complete Figure 3 a BSEI of a polished section with pinacoidal orientation of an ilmenite crystal showing three different exsolved phases (:) scarce disk shaped, white cassiterite lamellae, frequent tabular light gray manganocolumbite lamellae, both in three directions, and rounded, oval to irregular, ameboidal shaped, medium gray, hematite exsolution bodies, in the dark gray ilmenite host. The hematite exsolution bodies occur in two sizes, probably corresponding to two generations (scale bar 100 m). b Detail from a, showing the hexagonal arrangement of the manganocolumbite lamellae (arrow) and the difference in orientation between cassiterite and manganocolumbite lamellae (scale bar 50 m). c BSEI of a section nearly orthogonal to the pinacoid of another ilmenite crystal, with the manganocolumbite exsolution lamellae (light gray) in two directions in low angle with the hematite lamellae (medium gray) along the pinacoid (NNE in the photo). A large idiomorphic manganocolumbite inclusion( labeled with 7,in the lower part of the photo) and a large hematite lamella were formed by "collection recrystallization" as indicated by the lack of the smaller exsolution lamellae in the area surrounding the large inclusion (scale bar 100 m). Estudos Geológicos v. 16 (2), 2006 001 Estudos Geologicos Vol 16 - 2.p65 9 9 24/5/2007, 11:58 Manganocolumbite and cassiterite exsolution lamellae in ilmenite from the pitombeiras pagmatie... the B+C-sites to 9.000 (for easier comparison with other minerals, a 24 oxygen formula was used instead of the 32 oxygen formula required for the unit cell). The effectiveness of the Fe3+ correction procedure was checked by repeating some calculations using the method proposed by Droop (1987). Mineral chemistry Representative EMPA data are listed in Table 1. The number of acceptable quantitative analyses of the exsolved phases is not large because of the usually very small size of the exsolutions, very close of the size limit which warrantees the data to represent a single phase result (about 4 or 5 m), avoiding mix-analyses. Many other semiquantitative SEM and EMPA data are not included but confirm the main characteristics presented in Table 1 and Fig. 4a and b. The data of the chemical composition of the primary, exsolution bearing, type 1 ilmenite are very homogeneous. They have a content of 9.0 to 12.0 wt % of MnO, corresponding to 18 to 26 mol% of pyrophanite {(Mn/(Mn+Fe) vary between 0.18 to .26}. This Mn content is elevated in comparison with that one observed in the usual granitic ilmenites (between 2.0 and 7.0 wt% MnO according to Haggerty, 1976) and also higher than data from pegmatitic ilmenites reported by Uher et al. (1998), with 3.0 to 6,5 wt% MnO. The content of dissolved Nb2O5 + Ta2O5 in the ilmenite host varies from 1.4 to 3.4 wt. % (or 1 to 3mol% of columbite, considering the 2/1 relation of {(Nb+Ta}/{Fe+Mn} in the columbite group minerals and the variation of (Ta+Nb) content between 0.08 and 0.23 APFU, as listed in table 1}. The dissolved cassiterite content is of 0.03 to 0.25 wt% of cassiterite (ca. 0.1mol%). These values of dissolved columbite are below the maximal contents of 4.0 wt.% Nb2O5 + Ta2O5 in ilmenite referred to by „erný & Ercit (1989). 10 001 Estudos Geologicos Vol 16 - 2.p65 The alteration related, exsolution free, type 2 ilmenite has similar dissolved contents of Nb2O5 + Ta2O5 (1.4 to 2.13 wt%), than type 1 ilmenite, but smaller contents of tin. The chemical difference to type 1 ilmenite is much more noticeable because of the much higher contents of MnO in type 2 ilmenite (ranging from 15 to 29 wt% which corresponds to a pyrophanite content varying from 32 to 63 mol%). Values in this range are referred to by Haggerty (1976) to be restricted to ilmenites in peralkaline rock suites (7.0 to 30wt% MnO) or in Mn-ores. The increasing Mn content in this ilmenite in comparison with type 1 ilmenite, even being higher than usual in granites or pegmatitic ilmenites, is in agreement with its late stage formation, probably related to hydrothermal alteration. The deficit in Ti (always below the hypothetical stoichiometric value of 6.0 APFU, and lower than the sum of Fe+Mn+Fe3+ which always surpasses 6.0APFU) in both ilmenite types, indicate that there is a dissolved excess of hematite in the ilmenite (incomplete hematite exsolution in ferroan manganoan hemoilmenite), typical for ilmenites formed under high temperature conditions. The composition of the columbite group mineral exsolution lamellae indicates a classification as manganocolumbite {Ta/ (Ta+Nb) ranging from 0.06 to 0.10}, but very close to the limit between ferro- and manganocolumbite fields {(Mn/(Mn+Fe) ratio between 0.54 and 0.58} in the columbite group quadrangle (Fig. 4a). As the sum of Ti+Sn+Fe3++Sc APFU ranges between 1,12 and 2.05 (or 9 to 18 mol% of dissolved cassiterite+rutile+Sc+ Fe3+-bearing phases, in a 12 APFU formula), it is not possible to distinguish if the exsolved phase is a disordered titanian and scandian manganocolumbite or a scandian titanian ixiolite based on mineral chemistry. This is because the data overlap the limit between these two phases as suggested by Wise et al (1998) Estudos Geológicos v. 16 (2), 2006 10 24/5/2007, 11:58 Table 1 Representative EMPA data of ilmenite and its exsolution lamellae from Pitombeira pegmatite in the BPP. Mineral abbreviations: Mcl= manganocolumbite; Cst=cassiterite, Ilm=ilmenite; Ilm (Mn) = high manganoan ilmenite; Pyf = pyrophanite; Hmt = hematite; na = not analyzed; 0.00 = below detection limit; others = W, Th, Hf, Al, Na, K, Le, Ce, Pb, Ba, Bi, Sb, P, Si, F. Hartmut Beurlen, et al. Estudos Geológicos v. 16 (2), 2006 001 Estudos Geologicos Vol 16 - 2.p65 11 11 24/5/2007, 11:58 Manganocolumbite and cassiterite exsolution lamellae in ilmenite from the pitombeiras pagmatie... Figure 4 EMPA of ilmenite and its exsolution lamellae from the Pitombeira pegmatite in the BPP. a data distribution in the "columbite quadrilateral" Ta/(Ta+Nb) versus Mn/(Mn+Fe) APFU plot. The primary, exsolution bearing ilmenite distinguishes easily by lower Mn and Ta numbers from the later, secondary ilmenite. The exsolution lamellae of manganocolumbite have lower Ta and higher Mn numbers than the hosting ilmenite, while the cassilterite exsolution lamellae have higher Ta and lower Nb numbers; b in the ternary Nb,Ta / Ti,Sn / Fe,Mn APFU plot the position of the manganocolumbite exsolution lamellae close to the 10 mol% (Sn,Ti) content is evidenced, that corresponds to the transition between disordered columbite and ixiolite according to Wise et al. 1998. The ilmenite contents in the hematite exsolutions are shown to be 7 to 15 mol% (Ti,Sn) or 15 to 30% ilmenite in the hosting type 1 ilmenite (thus to be distisguished as a hemoilmenite composed by a ferrian ilmenite host and titan hematite exsolutions according to the nomenclature by Buddington 1963). In comparison the secondary, type 2 ilmenite is distinguished by nearly endmember manganoan ilmenite, with no excess of iron or manganese. 12 001 Estudos Geologicos Vol 16 - 2.p65 Estudos Geológicos v. 16 (2), 2006 12 24/5/2007, 11:58 Hartmut Beurlen, et al. as can bee seen in Fig. 4b. In two cases the Sc + Ti contents surpass the maximal limit of solubility for Sc and Ti admitted by these authors for disordered columbite, while the other three data are slightly below this limit. An identification by conventional X-ray diffraction after heating, which would be indicated according to „erný et al. (1998), is not possible in this case due to the small size of the exsolution lamellae. The hematite exsolution lamellae are characterized by high Ti contents (between 0.76 and 1.77 APFU Ti, or up to 30 mol% ilmenite) as only significant dissolved strange element, allowing to classify it as titanian hematite. Such high Ti contents are also typical for hematite exsolution lamellae in plutonic or high temperature metamorphic rocks (Haggerty 1976, Rumble III 1976). Unfortunately, the absence of coexisting tiatanomagnetite and the high Mn contents make temperature estimates impossible. The EMPA data distribution in the "columbite quadrilateral" [Ta/(Ta+Nb) versus Mn/(Mn+Fe) APFU plot] in Fig. 4a, allows a clear distinction of the primary, exsolution lamellae bearing ilmenite type 1 by lower Mn and Ta numbers (respectively Mn/ (Mn+Fe) and Ta/(Ta+Nb) from the later, secondary type 2 ilmenite in which no exsolution lamellae are observed. The exsolution lamellae of manganocolumbite have lower Ta and higher Mn numbers than the hosting ilmenite, while the cassiterite exsolution lamellae have higher Ta and lower Nb numbers. This is a fractionation behavior similar to that one observed between exsolutions of orthorhombic columbite group minerals in rutile host, in which Ta + Fe are fractionated in favor of the tetragonal rutile phase while Mn and Nb are fractionated in favor of the orthorhombic phase (Cerný et al. 1998). The data distribution in the ternary Nb,Ta / Ti,Sn / Fe,Mn APFU plot allow to observe the position of the manganocolumbite exsolution lamellae close to the 10 mol% (Sn + Ti) content which corresponds to the transition between disordered columbite (less than 10 mol %) and ixiolite according to Wise et al. (1998), as discussed above. In this diagram the ilmenite contents in the hematite exsolutions are shown to be 7 to 15 APFU% Ti (plus minor Sn) which corresponds to 15 to 30 mol% ilmenite in the hosting type 1 ilmenite. The composite crystals of type 1 ilmenite are thus to be distinguished as a hemo-ilmenite composed by a ferrian ilmenite host (ilmenite with an excess of 5 to 10mol% hematite) and titanhematite exsolutions according to the nomenclature by Buddington & Lindsley (1964). In comparison, the secondary, type 2 ilmenite is distinguished as nearly stoichiometric manganoan ilmenite, with a very small excess of iron. CONCLUSIONS Two types of ilmenites are distinguished as accessory opaque minerals of the Pitombeira pegmatite in the Borborema Pegmatitic Province. Type 1 ilmenite is distinguished by the unusual trellis like scandian manganocolumbite and cassiterite exsolution lamellae in association with hematite exsolution lamellae. The (Ta+Nb)2O5 content of the homogeneous primary magmatic ilmenite (precursor of the ilmenite with exsolutions) is estimated to vary form 3.0 to 4.5 wt. %, very close to the values referred to by Cerný & Ercit (1989) as maximal contents in Č pegmatitic ilmenites. The Mn content of this type 1 ilmenite is high (18 to 26 mol% pyrophanite) if compared with other ilmenite occurrences in pegmatites (Haggerty 1976, Uher et al. 1998). Type 2 ilmenite is formed in association with microlite and tantalian sphene as probable hydrothermal alteration product of "strüverite", and has higher Mn contents than type 1 ilmenite (up to 62mol% pyrophanite).This ilmenite should therefore be classified as pyrophanite, until now unknown in the BPP. The Ta number of type 2 Estudos Geológicos v. 16 (2), 2006 001 Estudos Geologicos Vol 16 - 2.p65 13 13 24/5/2007, 11:58 Manganocolumbite and cassiterite exsolution lamellae in ilmenite from the pitombeiras pagmatie... ilmenite is higher than that of type 1, which is in accordance with the hypothesis of its formation in late stages of crystallization. Acknowledgments This research was supported by CNPq (Brazilian Research Council) Grants 470199/ 01-6 and 352181/92-3, and CAPES grant AEX 0728/04-7. We are also indebted to Dr. W. Heinrich of the GeoForschungsZentrum Potsdam (GFZ) in Germany for the free use of the Microprobe facility, Prof. Dr. Bernardino R. Figueiredo Instituto de Geociências of the University of Campinas, Brazil (IGE-UNICAMP), and to O. Appelt and G. Rehde of the GFZ for the technical support during the microprobe analyses. REFERENCES Almeida, F.F.M., Melcher, G.C., Cordani, U.G., Kawashita, K., Vandoros, P. 1968. Radiometric age determinations from Northern Brazil. São Paulo. Soc Bras Geol Bol 17: 3-15. Antony, J.W., Bideaux, R.A., Bladh, K.W., Nichols, M.C. 1997. Handbook of Mineralogy.Volume III Halides, Hydroxides, Oxides. Mineral Data Publishing, Tucson, Arizona, USA, 597p. Araújo, M.N.C., Silva, F.C.A., Jardim de Sá, E.F. 2001. Pegmatite emplacement in the Seridó Belt, Northeastern Brazil: late stage tectonics of the Brasiliano Orogen. Gondwana Res. 4, 75-85. Araújo, M.N.C., Vasconcelos, P.M., Silva, F.C.A., Jardim De Sá E.F., Sá, J.M. 2005. 40Ar/39Ar geochronology of gold mineralization in Brasiliano strike-slip shear zones in the Borborema province, NE Brazil. Journ. South Am. Earth. Sci. 19, 445-460. Baumgartner, R., Moritz, R., Romer, R., Sallet, R. 2001. Mineralogy and U/Pb geochronology of beryl and columbo-tantalite pegmatites in the Serido pegmatite district, northeastern Brazil. In: A. Pi- 14 001 Estudos Geologicos Vol 16 - 2.p65 estrzynski et al. (eds), Mineral deposits at the beginning of the 21st century, Proceedings of the 6th biennial SGA meeting, Krakow, Poland, 26-29 August 2001, Balkema Rotterdam, (371-375). Baumgartner, R., Rolf, L., Romer, R.L., Moritz, R., Sallet, R., Chiaradia, M. 2006. Columbite tantalite-bearing granitic pegmatites from the Seridó Belt, NE Brazil: genetic constraints from U-Pb dating and Pb isotopes. Can. Mineral. 44, 69-86. Beurlen, H., Castro, C., Thomas, R., Da Silva, M.R.R., Prado-Borges, L.E . 2004. Strüverite and Scandium bearing titanian ixiolite from the Canoas Pegmatite (Acari – Rio Grande Do Norte) in the Borborema Pegmatitic Province, Ne-Brazil. Est. Geol. 14, 20-31. Beurlen, H., da Silva, M.R.R., Thomas, R., Soares, D.R., Olivier, P. 2007. Nb-Ta-(Ti-Sn)oxide mineral chemistry as tracers of rareelement granitic pegmatite fractionation in the Borborema Province, Northeast Brazil. Mineralium Deposita,. 42, in press. BRASIL (1998): Mapa Geológico do Estado do Rio Grande do Norte. Brasil, DNPM-CPRM/UFRN BRASIL (2002): Mapa Geológico do Estado da Paraíba. Brasil, DNPM-CPRM/CDRM. Buddington, A.F. & Lindsley, D.H. 1964. Irontitanium oxide minerals and synthetic equivalents. Journ. Petrology, 5: 310-356. „erný, P. & Ercit, T.S. 1989. Mineralogy of Niobium and Tantalum: crystal chemical relationships, paragenetic aspects and their implications. In: Moeller, P., Cerný, P., Saupé, F. 1989. Lantanides, Tantalum, Niobium. Springer, Heidelberg, p 27-79. „erný P, Ercit, T.S., Wise, M.A., Chapman, R., Buck, H.M. 1998. Compositional structural and phase relationships in titanian ixiolite and titanian columbitetantalite. Can Mineral., 36: 547-562. Craigh J.R. & Vaughan D.J. 1981. Ore microscopy and ore petrography. John Wiley & Sons, NY 406p. Estudos Geológicos v. 16 (2), 2006 14 24/5/2007, 11:58 Hartmut Beurlen, et al. Da Silva M.R.R., Höll, R., Beurlen H. 1995. Borborema Pegmatitic Province: geological and geochemical characteristics. Journ. South Am. Earth Sciences, 8: 355-364. Droop, G.T.R. 1987. A general equation for estimating Fe3+ concentrations in ferromagnesian silicates and oxides from microprobe analyses using stoichiometric criteria. Mineral Magaz. 51, 431-435. Ebert, H. 1969. Geologia do Alto Seridó. Recife, Brazil. SUDENE Serie Geol. Reg., 11: 120p. Ercit, T.S., Cerný, P., Hawthorne, F.C., Mc Cammon, C.A. 1992a. The wodginite group II: crystal chemistry. Can. Mineral., 30: 613-632 Ercit, T.S., Cerný, P., Hawthorne, F.C. 1992b. The wodginite group III: classification and new species. Can. Mineral., 30: 633-638. Haggerty, S.E. 1976. Opaque mineral oxides in terrestrial igneous rocks. In: Rumble III D (ed.) Oxide minerals. Rev. Mineral., 3: Hg 101-300. Ixer R. A. & Duller P.R. 1998. SME-Virtual atlas of opaque and ore minerals.www.smemet. org/opaque-ore/IX_id_.htm Jardim de Sá, E.F. 1994. A Faixa Seridó (Província Borborema, NE do Brasil) e seu significado geodinâmico na cadeia Brasiliana/Panafricana. Tese de Doutorado, UnB, 762p. Jardim de Sá, E.F., Legrand, J.M., McReath, I. 1981. Estratigrafia de rochas granitóides na Região do Seridó (RN-PB) com base em critérios estruturais. Rev. Bras. Geoc. 11: 50-57. Jardim de Sá, E.F., Legrand, J.M., Galindo, A.C., and Hackspacker, P.C. 1986. Granitogênese Brasiliana no Seridó: o maciço de Acari (RN). Rev. Bras.Geoc., 16: 95-105. Johnston Jr, W.D. 1945. Beryl-tantalite pegmatites of Northeastern Brazil. Geol. Soc. Amer. Bul. 56: 1015-1070. Legrand, J.M., Deutsch, S., Souza, L.C. 1991. Datação U/Pb e granitogênese do maciço Acari (RN). In SBG 14o Simp. Geol. Nordeste, Atas , Bol. 12:172-174. Mc Leod, C.R. & Chamberlain, J.A. 1969. Reflectivity and Vickers microhardness of ore minerals. Chart and tables. Geol. Surv. Can, paper, 68-64. Ramdohr, P. 1969. The ore minerals & their intergrowths. Pergamon-Akademie, Berlin, 1174p. Rolff, P.M.A. 1946. Minerais dos pegmatitos da Borborema. Rio de Janeiro, DNPM Div. Fom. Prod. Min. Bol. 78: 23-76 Rumble III, D. 1976Oxide minerals in mewtamorphgic rocks. In: Rumble III D (ed.) Oxide minerals. Rev. Mineral., 3: R.1-R.24. Uher, P., Cerný, P., Chapman, R., Hatar, J. Miko., O. 1998a. Evolution of Nb,Ta-oxide minerals in the Prasiva Granitic Pegmatites Slovakia. I: Primary Fe,Ti-rich assemblage. Can. Mineral. 36: 525-534. Uytenboogarth, W. 1951. Tables for microscopic identification of ore minerals. Hafner Publishing Co., NY, 242p. Van Schmus, W.R., Brito Neves, B.B., Williams, I.S. Hackspacher, P.C. Fetter, A.H., Dantas, E.L., Babinski, M. 2003. The Seridó Group of NE Brazil, a late Neoproterozoic pre- to syn-collisional basin in West Gondwana: insights from SHRIMP U-Pb detrital zircon ages and Sm-Nd crustal residence (TDM) ages. Prec. Res. 127: 287-327. Wise, M.A., Cerný, P., Felster, A.U. 1998. Scandium substitution in columbitegroup minerals and ixiolite. Can. Mineral. 36: 673-680. Estudos Geológicos v. 16 (2), 2006 001 Estudos Geologicos Vol 16 - 2.p65 15 15 24/5/2007, 11:58