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The Herberton Mineral Field in Northeast Australia hosts world class magmatic-hydrothermal Sn–W polymetallic deposits that are enriched in In. The Baal Gammon and Isabel deposits from the Herberton Mineral Field contains early tin, as cassiterite, overprinted by sulfide mineralization as chalcopyrite, sphalerite, galena, pyrrhotite, and stannite. We investigated the distribution of In in the sulfide ores from these two deposits, calculated the temperature of formation via sphalerite-stannite geothermometer, and deduced the physicochemical conditions favorable for enriching In in this mineralizing environment. The Baal Gammon deposit is dominated by chalcopyrite, with In contained in chalcopyrite, sphalerite, and stannite. The average In concentrations measured by EPMA in chalcopyrite, sphalerite, and stannite are 0.10, 0.68, and 0.92 wt%, respectively. Chalcopyrite, pyrrhotite, and sphalerite textures indicate that In incorporation occurred during exsolution from an intermediate solid solution of cubanite composition. The Isabel deposit is dominated by sphalerite associated with galena and contains only minor amounts of chalcopyrite. The average concentration of In in sphalerite from the Isabel deposit is 0.11 wt%. The stannite-sphalerite geothermometer indicates mineralization temperatures of ~ 290 °C at the Baal Gammon deposit, and ~ 307 °C at the Isabel deposit. At these temperatures, the physicochemical modeling suggests that stable In chlorine complexes occur in acidic conditions (pH < 3). These results when combined with the Eh–pH phase model of the sulfide assemblage further constrain the redox conditions during mineralization.
The Herberton Mineral Field in Northeast Australia hosts world class magmatic-hydrothermal Sn–W polymetallic deposits that are enriched in In. The Baal Gammon and Isabel deposits from the Herberton Mineral Field contains early tin, as cassiterite, overprinted by sulfide mineralization as chalcopyrite, sphalerite, galena, pyrrhotite, and stannite. We investigated the distribution of In in the sulfide ores from these two deposits, calculated the temperature of formation via sphalerite-stannite geothermometer, and deduced the physicochemical conditions favorable for enriching In in this mineralizing environment. The Baal Gammon deposit is dominated by chalcopyrite, with In contained in chalcopyrite, sphalerite, and stannite. The average In concentrations measured by EPMA in chalcopyrite, sphalerite, and stannite are 0.10, 0.68, and 0.92 wt%, respectively. Chalcopyrite, pyrrhotite, and sphalerite textures indicate that In incorporation occurred during exsolution from an intermediate solid solution of cubanite composition. The Isabel deposit is dominated by sphalerite associated with galena and contains only minor amounts of chalcopyrite. The average concentration of In in sphalerite from the Isabel deposit is 0.11 wt%. The stannite-sphalerite geothermometer indicates mineralization temperatures of ~ 290 °C at the Baal Gammon deposit, and ~ 307 °C at the Isabel deposit. At these temperatures, the physicochemical modeling suggests that stable In chlorine complexes occur in acidic conditions (pH < 3). These results when combined with the Eh–pH phase model of the sulfide assemblage further constrain the redox conditions during mineralization.
The Herberton Mineral Field hosts multiple small-scale, polymetallic Sn-Cu and Sn-Zn deposits. The Baal Gammon and Isabel polymetallic deposits in the Herberton Mineral Field contain early Sn that is overprinted by sulfides. At Baal Gammon, the sulfide overprinting is Cu-In-rich, whereas Isabel is a Zn-Pb-In-rich system. These deposits are hosted in the meta-sedimentary rocks of the Hodgkinson Formation and the porphyry dikes and volcanic rocks of the Kennedy Igneous Association. Primary Sn in these deposits occurs as cassiterite, which was altered to stannite during sulfide mineralization. The sulfide ores from Baal Gammon consist of chalcopyrite, pyrrhotite, and minor sphalerite, and sphalerite, galena, and minor chalcopyrite are observed at Isabel. Chalcopyrite from Baal Gammon contains on average 609 ppm Ag, 1194 ppm In, and 1410 ppm Sn, whereas chalcopyrite from the Isabel deposit contains on average 2302 ppm Ag, 725 ppm In, and 1042 ppm Sn. Sulfur isotope (δ34S) measurements of in-situ chalcopyrite-pyrrhotite mineral pairs show limited variation and low values that are indicative of a magmatic sulfur source with limited interaction with sulfur from connate and meteoric fluids during mineralization. The chalcopyrite and pyrrhotite δ34S values at the Baal Gammon deposit vary between 0.99–1.91‰ and 1.35–2.48‰, respectively. The δ34S values at the Isabel deposit vary between 0.91–1.45‰ for chalcopyrite and 1.12–2.11‰ for pyrrhotite. The trace element composition of major sulfides and sulfur isotopes of chalcopyrite and pyrrhotite combined with thermodynamic modeling indicates that the mineralizing fluids at the Baal Gammon and Isabel deposits have an igneous source, where the metals were transported as metal-chloride complexes at low pH (< 5) and below ~ 300 °C. The source of these sulfide-rich mineralizing fluids is most likely derived from the magmatic activity associated with the emplacement of the Slaughter Yard Creek Volcanics during a period of crustal thinning between 300 and 280 Ma.
The Lautenthal sphalerite-galena vein deposit is part of the world-class Upper Harz Pb-Zn-Ag district in the Harz uplift block of the Paleozoic Variscan fold belt in Germany. Its sphalerite-dominated mineral association was studied using bulk-ore chemistry, electron probe microanalysis, and laser ablation-ICP-mass spectrometry. Gallium and locally In are the main high-tech-relevant trace elements hosted by sphalerite, with up to 150 ppm Ga and up to 380 ppm In in hand-picked sphalerite samples (mean In/Zn, 0.70 × 10−3). Ore concentrates (≤ 50 kg) contain up to 65 ppm Ga and up to 109 ppm In (mean In/Zn, 0.36 × 10−3). Accessory Fe-Co-rich gersdorffite-1 occurs in the earlier quartz-sulfide ore stage and Sb-rich gersdorffite-2 in the later carbonate-sulfide stage. Enrichment patterns of In are either defined by overprinting textures in the Fe-richer sphalerite-1 of the earlier stage, or relate to primary growth zoning in Fe-poor sphalerite-2 of the later stage. Using the sphalerite geothermometer GGIMFis, formation temperatures (median) of sphalerite-1 were estimated at ~ 230 °C for the Lautenthal orebody and at ~ 175 °C for the Bromberg orebody, which may indicate lateral T-zonation for the earlier ore stage. Sphalerite-2 data indicate formation temperatures of ~ 185 °C (median). Copper-bearing brines of the carbonate-sulfide stage with assumed temperatures of ~ 250 °C initiated replacement of In-poor sphalerite-1 by chalcopyrite and remobilization of Zn and trace elements. Indium-rich sphalerite-2 occurs associated with calcite and fine-grained galena. A direct spatial or temporal link of ore formation to a magmatic-hydrothermal system is unlikely, which contrasts to In-rich epithermal and tin-polymetallic vein deposits worldwide.
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