A geochemical study of gallium, germanium and indium, in sulfide mineralisation of the Kombat, Tsumeb and Khusib springs deposits, Otavi Mountain Land, Namibia

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Date
2024
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University of Namibia
Abstract
Carbonate-hosted base metal deposits are known to contain significant contents of critical metals such as Ga, Ge, and In. These metals occur mainly as inclusions or incorporated within the crystal lattice of the main sulfide minerals while they form rarely discrete minerals. The aim of this Doctor of Philosophy (PhD) study is to determine the geochemical characteristics of the critical raw metals that are associated with the sulfide mineralisation of the base metal deposits of the Otavi Mountain Land, with the emphasis on the Tsumeb, Kombat and Khusib Springs deposits. Tsumeb mine is an over the decades exploited breccia-pipe like polymetallic deposit, hosted by Neoproterozoic dolomite and limestones in the Otavi Group of the Damara Orogenic Belt. Exploitation took place between 1897 and 1996, with a production of about 30 Mt of ore, yielding 1.7 Mt Cu, 2.8 Mt Pb, 0.9 Mt Zn, and 80 t Ge. Mineralisation at this deposit consists of tennantite and sphalerite as the most abundant ore minerals, associated with galena, pyrite, bornite, chalcocite, digenite, and minor enargite, renierite, germanite, chalcopyrite, and traces of various arsenates. Kombat deposit, which is a stratabound, syntectonic Cu-Pb (Ag) sulfide deposit, is hosted in the dolomite of the Hüttenberg Formation, Otavi Group. Mining of the Kombat deposit is currently ongoing, with a total endowment of approximately 13.6 Mt, of which 12 Mt has been exploited until 2008. The ore mineralisation of the Kombat deposit is quite variable comprising massive, disseminated, veinlet-controlled, and brecciated mineralisation styles with abundant bornite, chalcopyrite, galena, covellite, and chalcocite set into quartz-calcite gangue. Khusib Springs deposit is a high-grade Cu-Pb Zn deposit which is classified as a “Tsumeb-type deposit”, hosted by Neoproterozoic dolomite, limestone and phyllites of the Maieberg Formation, Otavi Group. The main aim of this study is to show the siting of the most important minor and trace elements in the diverse sulfide mineral phases and to highlight the relationships between common trace elements and critical metals within the sulfide mineral phases. Various analytical techniques, including laser ablation inductively coupled plasma spectrometry (LA-ICP MS), electron microprobe analysis (EPMA), inductively coupled plasma mass spectrometry (ICP-MS), and X-ray fluorescence (XRF), were employed to study the bulk ii geochemistry and the siting of the trace elements, for the sole purpose of answering the above-mentioned objectives. Additionally, portable X-ray fluorescence (pXRF) technique was utilized with the aim of evaluating the possible usability of a low-cost analytical technique in exploration for base and critical elements in carbonate-hosted sulfide mineralisations. The Kombat mineralization comprises three mineral assemblages (1) bornite-chalcopyrite-covellite, (2) bornite-galena-chalcocite, and (3) bornite-chalcopyrite, set into dolomite-quartz-calcite gangue, with chalcopyrite identified as the main carrier of Ga, Ge, and In in this deposit. The profound micro-analysis of Tsumeb ore revealed the presence of both Ga and Ge, associated with trace elements (Ag, As, Cd, Co, Cu, Fe, Ga, Ge, In, Ni, Pb, Sb, Zn), in the different sulfides. The most significant carriers of Ge are renierite (av. 8.21 wt.%) and enargite (0.78 wt.%), while Ga is mainly incorporated into renierite (av. 0.12 wt.%) and sphalerite (av. 0.11 wt%). Trace element abundance in sphalerite is characterized by elevated Cd, Ge, and Ga, suggestive of low formation temperatures, which corroborates with earlier research on the formation of Tsumeb ore. Reconnaissance Zn isotope data (-0.19 to 0.14‰) delineate Tsumeb ore as typical Zn-rich massive sulfide ore, with Zn isotope values overlapping with those of the Irish MVT deposits (-0.17 to 1.33‰), while Cu isotopes are comparable to isotopic data of hypogene mineralisation. In Khusib Springs ore, tennantite (Fe, Zn, Ag, Sb) and chalcopyrite (Cu, Pb, Ag) are the most important carriers of trace elements while all other sulfides are characterized by a surprisingly low trace element content. In contrast, Khusib Springs massive ore reveals a wealth of Ag-bearing minerals of the pearceite-polybasite mineral group. Modern portable tools are successfully applied for the analyses of selected elements in various fields. Portable XRF can be used as well for the analyses of selected elements (Cu, Fe, Mn, Pb, Zn) in Kombat-type ore, while these instruments fail for the analyses of elements like Ag, Sr, and, in particular, for the analyses of the target elements Ga, Ge, and In. Therefore, this study gives a detailed overview about the relationship between critical elements Ga, Ge, and In and associated elements in sulfide ores in the carbonate-hosted base metal deposits of the Otavi Mountain Land, while showing at the same time the limitations when access to modern analytical technologies is limited
Description
A dissertation submitted in fulfillment of the requirements for the Degree of Doctor of Philosophy in Science (Geology)
Keywords
Gallium, Germanium, Indium, Otavi Mountain Land, Sulfide mineralisation, Kombat deposit, Khusib Springs deposit, Tsumeb deposit, Trace elements
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