The formation of (Ni-Co-Sb)-Ag-As ore shoots in hydrothermal galena-sphalerite-fluorite veins

Unusual hydrothermal native As-sulfide ± native Ag ± arsenide ± antimonide ± sulfosalt ore shoots and their co-genetic sulfide-fluorite-barite-quartz host veins, which are common in the region and in whole Central Europe, were investigated at three localities in the Schwarzwald, SW Germany, to understand the physico-chemical processes governing the change from a normal (= common) hydrothermal to an exceptional ore shoot regime. Based on fluid inclusions, the formation of the gangue minerals is the result of binary mixing between a NaCl-rich brine and a CaCl2-rich brine (both ~ 20 wt% NaCl aq.). This mixing correlation, major and minor fluid composition, formation temperature (~ 150 °C), and δ34S signature are identical (within error) in ore shoots and host veins. Thermodynamic modeling indicates that ore shoot formation must have resulted from a change in redox conditions by a local influx of a volumetrically minor reducing agent, probably hydrocarbons. The elemental content and the mineralogy of each ore shoot locality (Ag-As-rich: Münstertal; Ag–Ni-As-rich: Urberg; Ag–Ni-As-Sb-rich: Wieden) reflect the metal content of the binary mixed fluid, while mineral textures, successions, and assemblages are thermodynamically and, regarding sulfur, kinetically controlled. The formation of vein and ore shoot sulfides requires an addition of sulfide, most probably from the sulfide-bearing host rocks, because thermodynamic and kinetic reasons suggest that the two major vein-forming and metal-bearing fluids are not the source of the sulfur. The final ore shoot textures are influenced by later hydrothermal remobilization processes of As and Ag. This results in a number of sulfosalts, mostly proustite-pyrargyrite. Interestingly, the greater thermodynamic stability of Sb-endmember sulfosalts enables them to form even in As-dominated fluid systems.