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Germanium- and gallium-rich sphalerite in Mississippi Valley–type deposits: the San Vicente district and the Shalipayco deposit, Peru

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Abstract

Sphalerite in Mississippi Valley–type (MVT) deposits hosts significant resources of both germanium and gallium. Here, we provide a survey on the distribution of Ge, Ga, and other minor and trace elements in sphalerite from MVT deposits in the Eastern Cordillera and sub-Andean regions of Peru, including the San Vicente deposit and the nearby Chilpes and Huacrash prospects, and the Shalipayco deposit. We present also a micro- and nano-scale textural characterization of Ge-rich sphalerite. In situ laser ablation-inductively coupled plasma-mass spectrometry analyses yielded Ge contents (inter-quartile range [IQR] = 164–36 ppm for the San Vicente district and IQR = 425–101 ppm for the Shalipayco deposit) that overlap with the range reported for sphalerite from other MVT deposits elsewhere. The highest Ge contents (IQR = 1207–375 ppm, up to 1861 ppm) were found in Fe-poor orange sphalerite deposited during a volumetrically minor second mineralization step in the San Vicente deposit located mainly in steep veins that crosscut the main first-step mineralization dominated by darker sphalerite. Reddish-brown sphalerite from Chilpes (IQR = 445–22 ppm, up to 1745 ppm) and brownish orange sphalerite from Huacrash (IQR = 650–34 ppm, up to 855 ppm) also yielded remarkably high Ge values. In Shalipayco, the highest Ge contents were analyzed in late Fe-poor yellow sphalerite (IQR = 375–267 ppm, up to 1119 ppm). The highest Ga contents were determined in reddish-brown sphalerite from the Chilpes prospect (IQR = 1156–0.26 ppm, up to 3943 ppm), although Ga contents are, in general, much lower than those of Ge in most analyzed sphalerite (IQR = 27–0.22 ppm in the San Vicente district and IQR = 2.8–0.081 ppm in the Shalipayco deposit). These figures place some of the analyzed sphalerite types among the Ge- and Ga-richest samples ever reported. Linkage of textural and compositional data points to light-colored, chiefly orange and yellow sphalerite generations crystallizing at lower temperatures and relatively late in the paragenetic sequences as those with the highest Ge contents. In contrast, the paragenetic control on Ga enrichment is unclear. Focused ion beam and high-resolution transmission electron microscopy (FIB-HRTEM) investigation combined with trace element content correlations reveal selective partitioning of Ge and Ga into sphalerite as structurally bound elements and their incorporation via substitution mostly coupled to monovalent cations triggering polytypism.

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Acknowledgements

We want to thank the staff of SIMSA-Unidad Minera San Vicente for the help and hospitality during sampling tasks and the Minera Nexa Resources for providing samples from the Shalipayco deposit. We appreciate the technical support by Xavier Llovet (CCiT-UB) during the acquisition of EMPA data and by Pete Tollan (ETH) during the acquisition of LA-ICP-MS data. Finally, we also would like to thank Alejandro Vargas (BIZALAB.SAC) for the SEM analyses. We are grateful to Frank Melcher, Associate Editor Hartwig Frimmel, and Editor-in-Chief Bernd Lehmann for their constructive comments which significantly improved the manuscript.

Funding

This study was economically supported by the Peruvian CONCYTEC-FONDECYT-World Bank project 107–2018-FONDECYT-BM-IADT-AV managed through the PROCIENCIA agency, and logistically suported by the project 2021 SGR 00239 of the Agència de Gestió d'Ajuts Universitaris i de Recerca de Catalunya.

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  1. Oscar Laurent

    Present address: CNRS, Géosciences Environnement Toulouse, Observatoire Midi-Pyrénées, 31400, Toulouse, France

Authors and Affiliations

  1. Geological Engineering Program, Faculty of Sciences and Engineering, Pontifical Catholic University of Peru (PUCP), Av. Universitaria 1801, San Miguel, Lima, 15088, Peru

    Lisard Torró, Andrea Julieta Millán-Nuñez, Diego Benites, Jean Vallance & Silvia Rosas

  2. Instituto Andaluz de Ciencias de la Tierra, CSIC-Universidad de Granada, Avda. de las Palmeras 4, 18100, Armilla, Granada, Spain

    José María González-Jiménez

  3. Department of Earth Sciences, Institute for Geochemistry and Petrology, ETH Zürich, Clausiusstrasse 25, 8092, Zürich, Switzerland

    Oscar Laurent, Lorenzo Tavazzani & Cyril Chelle-Michou

  4. Departament de Mineralogia, Petrologia i Geologia Aplicada, Facultat de Ciències de la Terra, Universitat de Barcelona, Martí i Franquès s/n, 08028, Barcelona, Spain

    Joaquín A. Proenza & Joan Carles Melgarejo

  5. Compañía Minera San Ignacio de Morococha S.A.A.(SIMSA), Calle Manuel Gonzales Olaechea 448, San Isidro, Lima, 15047, Peru

    Carlos Flores

  6. Department of Earth Sciences, University of Geneva, CH-1205, Geneva, Switzerland

    Lluís Fontboté

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Torró, L., Millán-Nuñez, A.J., Benites, D. et al. Germanium- and gallium-rich sphalerite in Mississippi Valley–type deposits: the San Vicente district and the Shalipayco deposit, Peru. Miner Deposita 58, 853–880 (2023). https://doi.org/10.1007/s00126-023-01160-4

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