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 CuZn 2 (In,Ga)S 4 . 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.

The presently increasing demand for rare earth elements (REE), particularly in high-tech and “green energy” applications, has led to global interest in the distribution, origins and formation conditions of REE deposits. The World’s first hard-rock REE sources, the polymetallic deposits of Bastnäsfältet in Bergslagen, central Sweden, were also the place of the original discovery of several REE and many of their host minerals. Similar deposits with high concentrations of REE occur along a > 100 km corridor in the region and they share a number of geological and mineralogical features; all comprising Palaeoproterozoic, skarn-hosted magnetite-REE mineralisation of ambiguous origin. Here we report oxygen isotope data for magnetite and quartz, and oxygen and carbon isotope data for carbonates from ten of these classic deposits, to model and assess their mode of origin. Combined with existing geological observations, the isotope results support an origin in a c. 1.9 Ga shallow-marine back-arc, sub-seafloor setting, where felsic magmatic-sourced, high-temperature fluids reacted with pre-existing limestone interlayers, leading to localised skarn formation and magnetite-REE-mineral precipitation. These findings help us to better understand the geological processes that have produced economic REE mineralisation and may assist future exploration for these critical commodities.

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