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Trace element geochemistry of sphalerite in contrasting hydrothermal fluid systems of the Freiberg district, Germany: insights from LA-ICP-MS analysis, near-infrared light microthermometry of sphalerite-hosted fluid inclusions, and sulfur isotope geochemistry

Abstract

The historic silver mining district of Freiberg (Germany) comprises hydrothermal vein-style mineralization of Permian and Cretaceous age. We compare sphalerite compositions with associated ore-forming fluids and constrain the behavior of critical metals such as In, Ge, and Ga in contrasting hydrothermal environments. Fluid inclusion studies reveal that the Permian veins formed due to boiling and cooling of a low-salinity (0 to 6% eq. w[NaCl]) magmatic-hydrothermal fluid at 350 to 230 °C. In contrast, Cretaceous veins formed by mixing of highly saline (17 to 24% eq. w[NaCl + CaCl2] and variable Na/(Na + Ca) ratios) brines at low temperatures (~ 120 °C). Sulfides of the Permian ore stage have a narrow range of δ34SVCDT from − 2.3 to + 0.9‰, while the sulfides of the Cretaceous stage have a large scatter and significantly more negative δ34SVCDT values (− 30.9 to − 5.5‰), supporting the different nature of the hydrothermal systems. Contrasting fluid systems and ore-forming mechanisms correspond to markedly different trace element systematics in sphalerite. Permian sphalerite is significantly enriched in In (up to 2500 μg/g In) relative to two sphalerite generations of Cretaceous veins. The latter have higher Ge (up to 2700 μg/g Ge) and Ga (up to 1000 μg/g Ga) concentrations. The observed trace element systematics of different sphalerite generations imply that In is enriched in high-temperature, low- to intermediate-salinity fluids with a significant magmatic-hydrothermal fluid component, while Ge and Ga are more concentrated in low-temperature, high-salinity crustal fluids with no obvious magmatic-hydrothermal affiliation.

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Acknowledgments

Andreas Massanek and Christin Kehrer (Geoscientific and Ore Deposit Collection, TU Bergakademie Freiberg) are thanked for providing ore samples. Helene Brätz (GeoZentrum Nordbayern, Friedrich-Alexander Universität Erlangen-Nürnberg) helped during the LA-ICP-MS analyses; we gratefully acknowledge her assistance and guidance. Many thanks to Harald Strauß (Westfälische Wilhelms-Universität Münster) for sulfur isotope analyses. Anne Jantschke (TU Dresden) is thanked for Raman laser analyses. Andreas Bartzsch, Roland Würkert and Michael Stoll (HIF), and Michael Magnus (TUBAF) are thanked for sample preparation. The geographic map of Germany is based on data generated with generic mapping tools, GMT 5 (https://www.soest.hawaii.edu/gmt/). We would like to thank Marie-Christine Boiron, Thomas Monecke, and associate editor H. Albert Gilg for their constructive comments and Bernd Lehmann for handling our manuscript.

Funding

We are greatly indebted to the Dr. Erich-Krüger-Foundation for funding the new instrumental setup in the Fluid Inclusion Laboratory of the Economic Geology and Petrology Research Group in Freiberg. The first author is funded by the Biohydrometallurgical Center for Strategic Elements (BHMZ) of the Dr. Erich-Krüger-Foundation, TU Bergakademie Freiberg.

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Bauer, M.E., Burisch, M., Ostendorf, J. et al. Trace element geochemistry of sphalerite in contrasting hydrothermal fluid systems of the Freiberg district, Germany: insights from LA-ICP-MS analysis, near-infrared light microthermometry of sphalerite-hosted fluid inclusions, and sulfur isotope geochemistry. Miner Deposita 54, 237–262 (2019). https://doi.org/10.1007/s00126-018-0850-0

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Keywords

  • Sphalerite
  • Indium
  • Germanium
  • Gallium
  • Critical metals
  • EPMA
  • LA-ICP-MS
  • Fluid inclusions
  • Near-infrared light microthermometry
  • Sulfur isotopes
  • Geothermometer
  • Erzgebirge