The Huari Huari deposit, Potosí Department in SW Bolivia, hosts polymetallic stratiform and vein mineralization of Miocene age with significant concentrations of the critical metal indium (In). Vein mineralization records document early crystallization of quartz and cassiterite followed by prominent associations of sulfides and sulfosalts. The earliest sulfide was arsenopyrite, followed by pyrrhotite, and progressively giving way to pyrite as the main iron sulfide, whereas Cu–Ag–Pb sulfosalts constitute late hypogene associations. Sphalerite is the chief ore mineral, and its crystallization is extended during most of the mineralization lifespan as evidenced by its initial cocrystallization with pyrrhotine, then with pyrite, and finally with Ag–Pb sulfosalts. The composition of sphalerite varies from early to late generations with a continuous decrease in FeS that attests to a decrease in temperature, which is constrained to vary from ~450 to <200 °C, and/or an increase in f(S2), both congruent with the described paragenetic sequence. Indium concentrated mostly in the structure of Fe-rich sphalerite (up to 3.49 wt. %) and stannite (up to 2.64 wt. %) as limited solid solutions with roquesite in the (Zn,Fe)S–Cu2FeSnS4–CuInS2 pseudoternary system. In sphalerite, In shows a strong positive correlation with Cu at Cu/In = 1, suggesting its incorporation via a (Cu+ + In3+) ↔ 2Zn2+ coupled substitution, and it does not correlate with Fe. In stannite, In shows a moderate, negative correlation with Cu and Sn, and an In3+ ↔ (Cu+ + ½ Sn4+) coupled substitution is suggested. Coexisting sphalerite and stannite yielded the highest In concentrations and crystallized at temperatures between 350 and 250 °C. Copper activity probably played a major role in the accumulation of In in the structure of sphalerite since In-bearing sphalerite coexisted with the deposition of stannite, shows high concentrations of Cu (up to 0.13 atoms per formula unit (a.p.f.u.)) in its structure, and hosts exsolutions of stannite and chalcopyrite. Distribution on the district scale of In suggests an input of hydrothermal fluids richer in Cu in the central position of the mineralizing system, represented by the Antón Bravo vein.

The Bolivian tin belt is a metallogenic province in the Eastern Cordillera of the Andes known for its Sn, W, Ag and base metal deposits. Cassiterite, which is a major constituent in many magmatic-hydrothermal ore deposits from the Bolivian tin belt, can incorporate dozens of elements within its crystal lattice, making it a useful geological tracer mineral, and also a potential host of critical elements. New U-Pb dating of cassiterite yields Late Triassic (Kellhuani deposit) and Late Oligocene to earliest Miocene (Viloco, Huanuni and Llallagua deposits) ages. These ages confirm that Sn mineralization in the Bolivian tin belt occurred at least in two separate events during two major magmatic episodes apparently triggered by mantle upwelling, decompression melting and basalt Man crip Wi ho Track ChangeClick here to access/download;Manuscript Without Track Changes;0_Gemmrrich et al_BTB_V3.doc 2 production promoting high heat flow into the overlying crust. The composition of studied hydrothermal cassiterite yields some geochemical trends that are attributed to its distance to the causative intrusion and/or level of emplacement. For example, cassiterite is generally enriched in Nb and Ta and yields higher Ti/Zr and Ti/Sc ratios in samples from xenothermal ore deposits located adjacent to intrusive complexes relative to shallow xenothermal and epithermal ore deposits. Therefore, these geochemical trends in cassiterite are useful tracers pointing to magmatic-hydrothermal centers. REE distribution in cassiterite was likely influenced by boiling processes, which resulted in tetrad-type irregularities. Cassiterite from the Bolivian tin belt is unattractive as a source for Nb (interquartile range [IQR] 4.84-0.037 ppm), Ta (IQR 0.0924-0.0126 ppm) and Ge (IQR 3.92-0.776 ppm). Some deposits, however, contain cassiterite relatively enriched in In (IQR 96.9-9.78 ppm, up to 1414 ppm) and Ga (IQR 92.1-3.03, up to 7437 ppm), that could constitute an attractive supplementary source for these elements in addition to sulfide minerals in the same deposits.

Bauxite deposits, traditionally the main source of aluminum, have been recently targeted for their remarkable contents in rare earth elements (REE). With ƩREE (lanthanoids + Sc + Y) concentrations systematically higher than ~ 1400 ppm (av. = 1530 ppm), the Las Mercedes karstic bauxites in the Dominican Republic rank as one of the REE-richest deposits of its style.The bauxitic ore in the Las Mercedes deposit is mostly unlithified and has a homogeneous-massive lithostructure, with only local cross-stratification and graded bedding. The dominant arenito-roundgrained texture is composed of bauxite particles and subordinate ooids, pisoids and carbonate clasts. Mineralogically, the bauxite ore is composed mostly of gibbsite and lesser amounts of kaolinite, hematite, boehmite, anatase, goethite, chromian spinel and zircon. Identified REE-minerals include cerianite and monazite-Ce, whose composition accounts for the steady enrichment in lightrelative to medium-and heavy-REE of the studied bauxites.Considering the paleo-geomorphology of the study area, we propose that bauxites in the Las Mercedes deposit are the product of the erosion and deposition of lithified bauxites located at higher elevations in the Bahoruco ranges. Based on the available data, we suggest a mixed lithological source for the bauxite deposits at the district scale: bedrock carbonates and an igneous source of likely mafic composition.

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