No abstract

The Penouta Sn-Ta deposit, in the northwest of Spain, is a greisenized granitic cupola where Ta minerals occur mainly as disseminations in a leucogranite body intruded in Precambrian–Lower Cambrian gneisses and mica-schists. This leucogranite is a medium- to fine-grained inequigranular rock consisting mainly of quartz, albite, K-feldspar and muscovite. Accessory minerals are mainly of spessartine, zircon, cassiterite, Nb-Ta oxides, monazite, xenotime, native bismuth and pyrite. The alteration processes were mainly albitization, muscovitization and kaolinitization.This leucogranite is peraluminous and P-poor, with 0.03–0.07 wt.% P2O5, 900–1500 ppm Rb, 30–65 ppm Cs, 120–533 ppm Li, 80–140 ppm Ta, 51–81 ppm Nb and up to 569 ppm of Sn.Mineralogical characterization of Nb-Ta oxide minerals was determined by X-ray diffraction, scanning electron microscopy, electron microprobe analysis and mineral liberation analysis. Mn-rich members of the columbite-group minerals (CGM) are the most common Ta-bearing phases, but microlite, wodginite, tapiolite and Ta-rich cassiterite occur also. CGM crystals are commonly zoned concentrically, with a Nb-rich core surrounded by a Ta-rich rim, with a sharp boundary between them. Convoluted zoning occurs also. Dissolution textures resulting from the corrosion of columbite and tantalite rims, in particular, are common. The Mn/(Mn + Fe) ratio varies between 0.33 and 0.97 and the Ta/(Ta + Nb) ratio between 0.07 and 0.93. Wodginite and microlite formed as late replacements of CGM and occur associated with tantalite and cassiterite. Subhedral to anhedral cassiterite crystals, usually up to 200 μm across, occur in two generations: the earlier one is Nb,Ta-poor whereas in the later generation, the Ta content can reach >9 wt.% of Ta2O5 and 1.7 wt.% of Nb. The presence of a fluid phase in the apical zone of the granite, probably related to the separation of a fluid/vapour of the melt, could explain the sponge-like textures, the Ta enrichment associated with these textures, the occurrence of Ta-enriched mineral phases (microlite and wodginite) and their common interstitial character.

A concentrate obtained from mining tailings containing mainly cassiterite and columbotantalite was reduced for the production of tin metal. The compounds CaCO 3 , Na 2 CO 3 , K 2 CO 3 , and borax were used as fluxes in the pyrometallurgical reduction smelting process, and graphite was employed as the reducing agent. The greatest recovery of Sn (>95%) was obtained when using CaCO 3 as the flux; the purity of Sn was 96%. A slag equivalent to 25% of the mass of the initial concentrate was produced during the recovery of the Sn. This contained 45% Nb 2 O 5 and Ta 2 O 5 , adding extra value to the mine tailings. The tin metal ingot was purified by electrorefining involving a tin and H 2 SO 4 electrolyte solution and a 101.9 A/m 2 current applied for 148 h. Under these conditions, 90 wt % of the Sn in the ingot was recovered at a purity of 99.97%.

The strategic importance of tantalum and its scarcity in Europe makes its recovery from low grade deposits and tailings interesting. In Penouta, the contents of Ta and Sn in old tailings from an Sn mine are of economic interest. Due to the relatively low grade of Ta of around 100 ppm, a detailed study of the mineralogy and liberation conditions is necessary. In this study, the mineralogy and the liberation characteristics of Sn and Ta ores of the Penouta tailings were investigated and compared with the current leucogranite outcropping ores. The characterization was conducted through X-ray diffraction, scanning electron microscopy, and electron microprobe. In addition, automated mineralogy techniques were used to determine the mineral associations and liberation characteristics of ore minerals. The grade of the leucogranite outcropping was found to be about 80 ppm for Ta and 400 ppm for Sn, and in the tailings used for the liberation study, the concentrations of Ta and Sn were about 100 ppm Ta and 500 ppm Sn, respectively. In both, the leucogranite outcropping and tailings, the major minerals found were quartz, albite, K-feldspar, and white mica. Ore minerals identified were columbite-group minerals (CGM), microlite, and cassiterite. The majority of CGM examined were associated with cassiterite, quartz, and muscovite particle compositions and cassiterite was mainly associated with CGM, quartz, and muscovite. The liberation size was 180 µm for CGM.

The La Canalita pegmatites in the Navasfrías Sn-W district, in Spain, are a group of Li-rich LCT rare-element pegmatites hosted by metamorphic rocks. It consists of several dikes up to 1 m thick, 16 m in length and of unknown depth that were mined during the 40s and 50s for tin. Here, we document the Ta-rich oxide minerals, such as those of the columbite-tantalite group, tapiolite-(Fe) and microlite. It is possible to distinguish a primary assemblage, formed of extremely Mn-rich columbite and tantalite, and microlite, the latter forming the host of columbite-(Mn) exsolution lamellae in the intermediate parts of the dikes. The influence of metasomatic fluids led to the formation of a lepidolite-albite late unit and the crystallization of a secondary assemblage consisting of tantalite-(Fe), tantalite-(Mn) and tapiolite-(Fe). Uranium-rich microlite (up to 6% wt. UO 2 ) is present in this assemblage, replacing tantalite. Subsequently, the entrance of hydrothermal fluids, probably mixed with metamorphic fluids, caused a partial greisen-like alteration of the pegmatite bodies and formed a second generation of microlite replacing tapiolite, with high Ca and Ta and low F contents. The lack of a chemically suitable protolith in the surrounding metamorphic rocks, combined with the mineralogical paragenesis containing U-rich microlite, together with the composition of the Sn, Nb and Ta oxide minerals of the pegmatite dikes, suggest that the Cadalso -Casillas de Flores batholith is the most probable source of the melts forming the La Canalita pegmatite dikes.