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Tese Acesso aberto (Open Access) Greisens e Epi-sienitos potássicos associados ao granito água boa, Pitanga (AM): um estudo dos processos hidrotermais geradores de mineralizações estaníferas(Universidade Federal do Pará, 2002-10-23) BORGES, Régis Munhoz Krás; DALL'AGNOL, Roberto; http://lattes.cnpq.br/2158196443144675Three stanniferous greisen types were characterized in the western border of Água Boa pluton, Pitinga mine (AM), associated with the rapakivi granite facies: greisen 1 (Gsl), composed mainly by quartz, topaz, brown siderophyllite and sphalerite; greisen 2 (Gs2), composed essentially by quartz, phengite and chlorite; greisen 3 (Gs3), composed of quartz, fluorite and phengite, with minor green siderophyllite. Besides these rocks, a potassic episyenite (EpSK) was identified associated with the Gs2. In spite of the compositional and petrographic differences, all of these hydrothermal rocks derived from a same protholith, a hornblende biotite aikali feldspar granite to syenogranite. The Gsl shows an inner mineralogical zoning defined by topaz or siderophyllite predominance. Along drill cores, the siderophyllite-rich zone occurs near the contact with the greisenized grafite and the topaz-rich zone is situated far from the grafite contact. The brown siderophyllite displays moderated Al contents, and its compositional changes can be explained by Fe+2 substitution for A1+3 and Li in octahedral sites, with a coupled Al+3 substitution for Si+4 in tetrahedral sites. The mineralogical zones in the Gs2 are physicaliy separated in leveis with phengite or chlorite predominance. The mica of Gs2 is a phengite, whose chemical variation is due to substitution of viAl for Fe+2, coupled with Si+4 enrichment. The calculated Li contents in phengites are lesser than those estimated in siderophyllite. The green siderophyllite from Gs3 is VIAl richer and F poorer than Gs1 brown siderophyllite, and the phengite displays two compositional types: an early Fe+2-poor aluminous phengite and a later Fe+2- F-rich one whose chemical variation is similar to that of Gs2 phengite. The chlorite from the three greisen is a Fe-rich daphnite, and its compositional range is due to VIAl substitution for R+2 cations, coupled with Si+2 enrichment. The aluminous chlorite displays higher temperature formation than ferrous one, according to the geothermeter proposed in the literature. The Pitinga greisens were formed by different processes of interaction among three main fluids: (1) low salinity, F-rich, aquo-carbonic fluid, with initial temperatures between 400° -350°C, present during Gsl and Gs3 formation; (2) low salinity aqueous fluid, with a temperature around 300°C, which during a progressive salinity increasing process, originates a moderate to high salinity residual fluid, with temperatures between 200° - 100°C, present during the Gs2 formation and silicification stage of EpSK; (3) low salinity aqueous fluid, with temperatures between 200° - 150°C, which interplayed with the others two fluids in differents grades, contributing to the formation of ali the hydrothermal rocks. The first two fluids has seemingly an orthomagmatic origin while the latter has a surface characteristic (meteoric water?). Moreover, the data suggests that the fluid responsible by the initial stage of the episyenitization process was not registered in the studied samples. These fluids were trapped in pressure conditions around 1 Kbar, representing high crustal levels conditions, similar to that of the stanniferous granites from Pitinga. Both episyenitization and greisenization processes occurred without volume changes in the granitic protholith, and the density differences of the altered rocks were caused by the mass variations along the alteration processes. The greisenization process caused a extensive loss of Na2O and K2O, while SiO2 showed a immobile behaviour in Gsl but was parcially removed in Gs2. The Al2O3 was depleted during the Gs2 formation but added in Gsl. The Fe2O3 (Fe total), Sn, S, volatiles LOl and F were the responsible by the mass increase at greisenization. In the Gsl, the chemical changes in the fiuids were caused by F activity decrease and fO2 increase during cooling. These changes also originated the differentiation between the ZT, in the inner portions of the fratures/conducts, and the ZS, nearest to surrounding gravite. The Gs3 was formed in more oxidizing conditions by F-poorer fiuids than those trapped in the ZS. The dissolution cavities generated during the episyenitization process increased the permeability of the altered rocks, providing an increase of fluid/rock ratios in the EpSK and Gs2 sites. The interaction between aqueous fluid and EpSK feldspar, during the Gs2 formation, caused a continuous salinity increase. The ZF was formed in the early stages of this interaction, at higher temperatures, while the ZC was originated by the more cold and saline, residual fluid. The latter was also trapped in the quartz filling cavities in the EpSK during the later silicification stage. In this way, the greisens and the potassic episyenites were generated from interactions among, at least, three fluids of seemingly independent origin, from a same protholith, in shallow crust conditions. The fO2, F activity and salinity variations, during the hydrothermal system cooling, and the contrast in fluid/rock ratios caused by permeability differences, were very important factors to greisen differentiation. These factors controlled greatly the fluids compositional changes, and caused the cassiterite and sulphides precipitation in the greisens and the Sn- S-enrichment during later greisenization of EpSK.Tese Acesso aberto (Open Access) Petrologia de granitos alcalinos com alto flúor mineralizados em metais raros: o exemplo do Albita-granito da mina Pitinga, Amazonas, Brasil(Universidade Federal do Pará, 2000-11-23) COSTI, Hilton Túlio; DALL'AGNOL, Roberto; http://lattes.cnpq.br/2158196443144675The mineral deposits of the Pitinga mine are related to the Proterozoic Água Boa and Madeira granites. Both are intrusive in the 1888 ± 3 Ma old acid volcanic rocks of the lricoumé Group. The Madeira Granite is composed by four facies, which emplacement sequence was inferred from its field relationships. The early facies is an 1824 ± 2 Ma old, porphyritic, metaluminous amphibole biotite syenogranite, which locally shows rapakivi texture. This facies is followed by an 1822 ± 1 Ma old, equigranular, peraluminous alkali feldspar biotite gravite. The two late facies are an 1818 ± 2 Ma old porphyritic, hypersolvus, alkali feldspar grafite and subsolvus albite gravite. Contact relationships indicate that the liquids forming these two late phases coexisted during the magmatic stage. This implies that they were emplaced almost simultaneously and also that the albite gravite and the hypersolvus grafite have a similar age. The albite gravite is composed by two facies. The dominant is a gray, peralkaline core facies (CAbG), which is composed essentially by albite, quartz and K-feldspar, accompanied by cryolite, zircon, polylithionite, riebeckite, Li-Fe mica, cassiterite, pyrochlore and magnetite. The modal proportions of the essential phases are similar, suggesting a magmatic origin for the CAbG and a cotectic or near minimum composition for its melt. Other features indicating a magmatic origin for the CAbG are: (1) the common occurrence of microscopic snowball textures; (2) it's petrographic and geochemical homogeneous character; (3) local presence of associated rocks with fluidal or pegmatitic textures. The CAbG is transitional to a reddish, peraluminous border facies (BAbG), found along the contacts of the albite with the early facies of the Madeira Granite. The BAbG is composed by albite, quartz and K-feldspar, with subordinate amounts of fluorite, zircon, chlorite, cassiterite, hematite, and columbite. The BAbG modal proportions of the essential phases are more variable and it has higher quartz and lower albite modal contents compared with the CAbG. The BAbG was originated by the autometasomatic alteration of the CAbG. The fluids involved in this process had a strongly oxidizing character and associated chemical changes destabilized the peralkaline mineralogy of the CAbG as evidenced by the replacement of cryolite, micas, pyrochlore and riebeckite. EMPA analyses indicate that the feldspars of the CAbG have near end-member compositions. The K-feldspars (Or —98%) are not perthitic and show high contents of Rb20 (-2%) and Fe2O3 (-0.6%), while the albites (Ab —99%) show anomalously high Fe2O3 (-1%) and relatively low Al2O3. These compositional characteristics indicate: a final crystallization temperature around 500°C or lower for the CAbG; the Al2O3 depleted character of the CAbG melt. Two micas were identified in the CAbG, both showing extremely low K/Rb ratios and high contents of Fe, Zn e Li. The more abundant is a Zn-Rb-polylithionite and the other is dark, Fe-Li mica with high Zn, F and Rb contents. The latter is relatively impoverished in Al2O3 and has Fe in tetrahedral positions, being tentatively classified as a tetra-ferri-Li mica. The unusual chemical compositions of micas and feldspars, as weli as the associated Sn, Nb, Zr, F, mineralization indicate that the CAbG derived from a melt that was geochemically similar to those forming fractionated, rare metal NYF pegmatites. The high Fe2O3 in feldspars and high Fe2O3/FeO in the dark mica, besides the presence of magnetite in the CAbG, suggests that it crystallized under relatively oxidizing conditions (-NINO). The CAbG shows very high contents of F, Na2O, Sn, Nb, Zr, U, Th, Zn, Li and Rb, and low CaO, MgO, TiO2, P2O5, Ba, and Sr. K/Rb and Rb/Sr ratios display extreme values, demonstrating the advanced fractionation of the liquid that originates the CAbG. The gullwing-shaped REE patterns and very low LaN/YbN ratios indicate the strong influence of F during magmatic evolution. The REE are distributed as M-type tetrads, showing that the fractionation mechanisms and the distribution of the REE's were controlled by processes similar to those observed in rare metal-bearing, evolved granitic systems. The Nd isotopes indicate crustal Paleoproterozoic protholiths for the two early facies of the Madeira Granite, which shows slightly negative εNd values. The CAbG and one sample of the hypersolvus grafite show low, positive εNd values. These data can be interpreted as indicating that: (1) the albite granite and the hypersolvus grafite have a protholith which is distinct from that of the earlier facies of the Madeira Granite; (2) both group of rocks derived from a same protholith but the Sm-Nd isotopic system of the albite granite and hypersolvus grafite was disturbed. Ali analyzed samples of the BAbG and an oxidized sample of the hypersolvus grafite shows strongly negative and scattered εNd values. This suggests that the hydrothermal processes that affected these rocks were able to strongly disturb their Nd isotopic system. The adopted petrogenetic nnodel, based on experiments on the system albite grafite -H20 - HF at 1 Kbar, suggests that the albite granite was originated from residual liquids derived from pristine F-rich, MgO-, TiO2--, CaO-depleted magmas. The very high F contents of the residual liquids strongly depressed the viscosity, density and the solidus of the system. This permitted a extreme fractionation of the melt, which evolved in a temperature interval coincident with those of pegmatitic processes. Due to the increase of the H2O contents in the residual liquid in the inner portions of the albite grafite, water saturation was attained and an aqueous fluids was segregated allowing the formation of pegmatitic rocks, while the F-rich residual melt phase generated the veins and pods of massive cryolite.Dissertação Acesso aberto (Open Access) Química mineral em xenotímio e minerais associados as fases pegmatóides da facies albita-granito, Suíte Madeira, mina Pitinga, Amazonas.(Universidade Federal do Pará, 2013-08-05) SOLEDADE, Gilvana Lima da; COSTI, Hilton Tulio; http://lattes.cnpq.br/4331565632387516; LAMARÃO, Claudio Nery; http://lattes.cnpq.br/6973820663339281The Pitinga Mine is located in the northern state of Amazonas. In this area, the plutons Pitinga, Madeira, Água Boa and Europa, grouped in Madeira Suite, were dated in the Paleoproterozoic. The Madeira Granite contains four distinct facies: amphibolebiotitesyenogranite, biotite alkali feldspar granite, porphyritic hypersolvus alkali feldspar and last phase is the albite-granite, a rock strongly mineralized in rare metals and associated with pegmatites. The pegmatites have well developed crystals of quartz, potassic feldspar, albite, dark mica, cryolite, opaque minerals and xenotime, this last subject of this study. The geochemistry of the rocks belong to Madeira Granite showed that the albite-granite equigranular core (ABGN) has REE concentrations ranging from 187.43 to 328.03 ppm, reaching 1276.63 in the fluidal ABGN, and 6916.07 ppm in pegmatites. The yttrium concentrations ranging from 48.80 to 128.80 at ABGN, from 83.30 to 240.60 ppm in the fluidal ABGN and 1193.40 ppm in pegmatites. The xenotime, main HREE and Y mineral ore presented HREE content of 32% to 36% and Y of 21 to 25%. The distribution of ETR on xenotime is different from that observed in the equigranular ABGN, fluidal ABGN and in the pegmatite with strong enrichment in HREE, which suggests their late crystallization from highly differentiated and fractionated fluids, however, all patterns exhibit tetrad distribution type with high levels in HREE compared to LREE. Studies by SEM / EDS in the xenotime crystals revealed mineralogical associations and unusual textural patterns, not observed in optical microscopy, such as: exsolution features of thorite (ThSiO4) and gagarinita [NaCaY (F, Cl) 6], fractures filled by galena, cassiterite, micas and cryolite. Chemical analysis by WDS in highly altered areas and less altered areas in xenotime crystals revealed significant chemical differences in the gagarinite and thoriteexsolutions belong high altered portions when compared to the less altered and unchanged portions. The altered areas showed lower levels of SiO2 and ThO2 (average 0.05% and 0.06%, respectively) compared to those portions with incipient alteration (average 0.40% SiO2 and 0.62% of ThO2), reaching a maximum of 1.50% ThO2. The exsolution of thorite in xenotime, and differences in the compositional contents of Th and Si, in altered and unaltered portions of the crystal, show remobilization of these chemical elements in the altered areas of the crystal, where Th incorporated into the xenotime is exsolved, precipitating as thorite. The association xenotime-gagarinite is unprecedent in in the context of mineralization of Pitinga mine and it is first documented in this work, indicating that the gagarinite is not limited cryolite veins and associated to fluocerite. In the xenotime, the gagarinite occurs as oriented exsolved granules (altered areas) and as inclusions (subhedral to euhedral crystals) and thorite as oriented exsolved granules. The Pitinga Province is responsible for 60% of tin Brazilian production, with reserves associated to Sn Nb, Ta and F, beyond anomalous concentrations of Zr, Y, Rb and Th Adding to these reserves, the HREE oxides, also present in the pegmatite with xenotime, gagarinite and cryolite, enable the exploitation of these minerals as byproducts.
