Basement aquifer evolution and the formation of unconformity-related hydrothermal vein deposits: LA-ICP-MS analyses of single fluid inclusions in fluorite from SW Germany

The main ore stage of three similar unconformity-related vein systems in the Schwarzwald, SW Germany spanning a period of activity of ~150 Ma, was investigated to understand the details of fluid penetration from overlying sediments/marine environment into the basement, their evolution as well as the processes involved in vein formation. To investigate temporal and spatial variations of the hydrothermal fluids responsible for mineralization, over 1650 fluid inclusions were analyzed by microthermometry. Of these, a total of 108 fluid inclusions (mainly in fluorite) were successfully analyzed by LA-ICP-MS. The fluid inclusions reveal a binary mixing trend between a CaCl2- and a NaCl-rich endmember. Independent of major element composition, the fluids are metal-bearing (e.g., up to ~100 mg/kg Ba, Pb, Zn, Ni and up to 10 mg/kg Ag), show high As (up to 1000 mg/kg) and low S (below the detection limit in most analyses). Over time, the mixed fluid shows a gradual decrease in CaCl2 and increase in NaCl with slightly decreasing total salinity. Based on earlier studies and geochemical arguments, the veins formed by anisothermal binary fluid mixing of two fluids, which both were originally derived from seawater and chemically modified through interaction with the basement and sedimentary rocks in different ways. This produced a gradual stratified basement fluid reservoir comprising a modified bittern/halite dissolution brine. The fluids involved in the vein formation are sourced from different depths of this modified bittern/halite dissolution basement brine reservoir: fluid A, a CaCl2-dominated, KCl-poor, deeper seated brine with a salinity of ~25 wt% CaCl2 + NaCl, and fluid B, an NaCl-dominated and KCl-richer brine situated at shallower depths in the crystalline basement with salinities of ~22 wt% NaCl+CaCl2. Based on the Na-Ca-K and NaK thermometers and on Rb/Cs systematics, fluid A records alteration of the Na-, K- and Ca-bearing feldspars of the host rocks; progressive alteration led to consumption of mainly Ca-rich plagioclase in contact with these basement brines. Accordingly, fluid B that subsequently entered the basement was only in equilibrium with alkali feldspars and clay minerals. This scenario produced a gradual change of fluid composition with depth that was pushed to greater depth over time. The source temperatures are estimated to ~250 °C while vein formation occurred at 100–170 °C, based on fluid inclusion homogenization temperatures. Thus, significa