Germanium speciation in experimental and natural sphalerite: Implications for critical metal enrichment in hydrothermal Zn-Pb ores

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dc.contributor.authorLiu, WHen_AU
dc.contributor.authorMei, Yen_AU
dc.contributor.authorEtschmann, BEen_AU
dc.contributor.authorGlenn, Men_AU
dc.contributor.authorMacRae, CMen_AU
dc.contributor.authorSpinks, SCen_AU
dc.contributor.authorRyan, CGen_AU
dc.contributor.authorBrugger, Jen_AU
dc.contributor.authorPaterson, DJen_AU
dc.date.accessioned2024-10-03T21:56:58Zen_AU
dc.date.available2024-10-03T21:56:58Zen_AU
dc.date.issued2023-02-01en_AU
dc.date.statistics2024-10-04en_AU
dc.descriptionResearch funding is from the Commonwealth Scientific and Industrial Research Organisation (CSIRO) to W. L., CSIRO’s Deep Earth Imaging Future Science Platform to YM, and the Australian Research Council Discovery grant DP220100500 to J.B. The molecular simulation of this work was supported by resources provided by the Pawsey Supercomputing Centre with funding from the Australian Government and the Government of Western Australia, and the high-performance computers in CSIRO. Part of this research was undertaken on the XFM beamline at the Australian Synchrotron, part of ANSTO. We thank Associate Editor Prof. M. Reich, an anonymous reviewer and Dr. A Perez-Fodich for their helpful reviews.en_AU
dc.description.abstractThe critical metal germanium (Ge) is recovered as a by-product of mining other commodities, such as zinc and thermal coal. We investigated the Ge incorporation mechanism in sphalerite synthesized under hydrothermal conditions like those of sediment-hosted Zn-Pb deposits. Sphalerite ± galena ± barite formed via reactions of Ge ± Fe ± Cu ± Ba-bearing brine with calcite and reduced sulfur at 200 °C and water vapor-saturated pressure. The products were examined using backscattered electron (BSE) imaging, electron probe microanalysis (EPMA), electron backscattered diffraction (EBSD), synchrotron X-ray fluorescence (SXRF) and micro-X-ray absorption near-edge structure (μ-XANES). We show that Ge(IV) is incorporated into sphalerite and bonded with reduced sulfur, both in the experimental sphalerite and in natural zinc ore samples from the MacArthur River Zn-Pb-Ag deposits, Australia. Copper K-edge XANES spectra show that copper occurs as Cu(I) in the experimental sphalerite, consistent with previous studies on Cu in natural sphalerite. The experiments reveal that Ge(IV) substitution in sphalerite occurs with and without the presence of other metal ions (e.g., Cu(I)), indicating that Ge(IV) substitution can be accommodated via charge balance by vacancies as well as by coupled substitution in the synthesized sphalerite. Ab initio quantum chemical simulations confirm that sphalerite can readily accommodate Ge via charge balance by vacancies and by coupled substitutions, with the crystal structure and average Zn-S, Zn-Zn, S-S distances retained when replacing > 3 mol% of the Zn sites with Ge(IV), Ge(II), Cu(I) or Fe(II), demonstrating the resilience and flexibility of the sphalerite crystal structure. These Ge incorporation mechanisms explain the previous observations of multiple ways of Ge incorporation in natural sphalerite. The study provides experimental and molecular simulation insights for understanding the processes related to the formation and extraction of Ge in zinc ores. 2022 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-NDlicenseen_AU
dc.identifier.citationLiu, W., Mei, Y., Etschmann, B., Glenn, M., MacRae, C. M., Spinks, S. C., Ryan, C. G., Brugger, J., & Paterson, D. J. (2023). Germanium speciation in experimental and natural sphalerite: Implications for critical metal enrichment in hydrothermal Zn-Pb ores. Geochimica et Cosmochimica Acta, 342, 198-214. doi:10.1016/j.gca.2022.11.031en_AU
dc.identifier.issn0016-7037en_AU
dc.identifier.journaltitleGeochimica et Cosmochimica Actaen_AU
dc.identifier.pagination198-214en_AU
dc.identifier.urihttp://dx.doi.org/10.1016/j.gca.2022.11.031en_AU
dc.identifier.urihttps://apo.ansto.gov.au/handle/10238/15712en_AU
dc.identifier.volume342en_AU
dc.languageEnglishen_AU
dc.language.isoenen_AU
dc.publisherElsevieren_AU
dc.subjectGermaniumen_AU
dc.subjectMineralsen_AU
dc.subjectSedimentsen_AU
dc.subjectZincen_AU
dc.subjectLeaden_AU
dc.subjectDepositsen_AU
dc.subjectX-ray fluorescence analysisen_AU
dc.subjectBackscatteringen_AU
dc.subjectAustraliaen_AU
dc.titleGermanium speciation in experimental and natural sphalerite: Implications for critical metal enrichment in hydrothermal Zn-Pb oresen_AU
dc.typeJournal Articleen_AU
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