The In-Ga-Sb association of the post-Variscan Zn-Pb-Ag vein deposit at Lautenthal, Upper Harz Mountains, Germany: sphalerite mineral chemistry

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.