Abstract

Germanium, gallium and indium are in high demand due to their growing usage in high-tech and green-tech applications. However, the mineralogy and the mechanisms of concentration of these critical elements in different types of hydrothermal ore deposits remain poorly constrained. We investigated the mineralogical distribution of Ge, Ga and In at the Mt Carlton high-sulfidation epithermal deposit in NE Australia, using electron probe microanalysis and laser ablation inductively-coupled plasma mass spectrometry. Parageneses from which selected minerals were analyzed include: Stage 1 acid sulfate alteration (alunite), Stage 2A high-sulfidation enargite mineralization (enargite, argyrodite, sphalerite, pyrite, barite), Stage 2B intermediate-sulfidation sphalerite mineralization (sphalerite, pyrite, galena) and Stage 3 hydrothermal void fill (dickite). Moderate to locally high concentrations of Ga were measured in Stage 1 alunite (up to 339 ppm) and in Stage 3 dickite (up to 150 ppm). The Stage 2A ores show enrichment in Ge, which is primarily associated with argyrodite (up to 6.95 wt % Ge) and Ge-bearing enargite (up to 2189 ppm Ge). Co-existing sphalerite has comparatively low Ge content (up to 143 ppm), while Ga (up to 1181 ppm) and In (up to 571 ppm) are higher. Sphalerite in Stage 2B contains up to 611 ppm Ge, 2829 ppm Ga and 2169 ppm In, and locally exhibits fine colloform bands of an uncharacterized Zn-In mineral with compositions close to CuZn2(In,Ga)S4. Barite, pyrite and galena which occur in association with Stage 2 mineralization were found to play negligible roles as carriers of Ge, Ga and In at Mt Carlton. Analyzed reference samples of enargite from seven similar deposits worldwide have average Ge concentrations ranging from 12 to 717 ppm (maximum 2679 ppm). The deposits from which samples showed high enrichment in critical elements in this study are all hosted in stratigraphic sequences that locally contain carbonaceous sedimentary rocks. In addition to magmatic-hydrothermal processes, such rocks could potentially be important for the concentration of critical elements in high-sulfidation epithermal deposits.

Highlights

  • Germanium (Ge), gallium (Ga) and indium (In) are three commodities which have become increasingly sought-after in recent years

  • The present study focuses on key minerals formed throughout the paragenetic sequence at Mt Carlton, including minerals formed during Stage 1 acid sulfate alteration, Stage 2A high-sulfidation mineralization, Stage 2B intermediate-sulfidation mineralization and Stage 3 hydrothermal void fill

  • Contrary to the results presented in this study, the highest Ge concentrations in these chimneys were observed in pyrite and marcasite

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Summary

Introduction

Germanium (Ge), gallium (Ga) and indium (In) are three commodities which have become increasingly sought-after in recent years. Minerals 2017, 7, 213 optics (Ge) and solar cells (Ge, Ga, In) [1,2,3,4,5] Due to their increasing economic importance combined with current supply security risks, Ge, Ga and In are commonly classified within the group of critical raw materials [6]. These elements can be concentrated in a variety of hydrothermal ore deposits, including volcanic hosted massive sulfide (VHMS) deposits, Mississippi Valley-type (MVT) deposits, carbonate-hosted polymetallic deposits of Tsumeb-type (exemplified by Tsumeb in Namibia, Kipushi in D.R. Congo and the Apex Mine in Utah; e.g., [7]), syngenetic or early diagenetic sedimentary exhalative (SEDEX) deposits, epithermal deposits, polymetallic (±Sn) vein or stockwork deposits linked to granites, and skarn deposits [1,7,8].

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