Barite-pyrite mineralization of the Wiesbaden thermal spring system, Germany: a 500-kyr record of geochemical evolution

Barite-(pyrite) mineralizations from the thermal springs of Wiesbaden, Rhenish Massif, Germany, have been studied to place constraints on the geochemical evolution of the hydrothermal system in space and time. The thermal springs, characterized by high total dissolved solids (TDS) contents and predominance of NaCl, ascend from aquifers at 3-4 km depth and discharge at a temperature of 65-70degC. The barite-(pyrite) mineralization is found in upflow and discharge zones of the present-day thermal springs as well as at elevations up to 50 m above the current water table. Hence, this mineralization style constitutes a continuous record of the hydrothermal activity, linking the past evolution with the present state of this geothermal system. The sulphur isotope signatures of the mineralization indicate a continuous decrease of the δ³⁴S of sulphate from +16.9‰ in the oldest barite to +10.1‰ in the present-day thermal water. The δ³⁴S values of barite closely resemble various recently active thermal springs along the southern margin of the Rhenish Massif and contrast strongly with different regional ground and mineral waters. The mineralogical and isotopic signatures, combined with calculations based on uplift rates and the regional geological history, indicate a minimum activity of the thermal spring system at Wiesbaden of about 500 000 years. This timeframe is considerably larger than conservative models, which estimate the duration of thermal spring systems in continental intraplate settings to last for several 10 000 years. The calculated equilibrium sulphur isotope temperatures of coexisting barite and pyrite range between 65 and 80degC, close to the discharge temperature of the springs, which would indicate apparent equilibrium precipitation. Kinetic modelling of the re-equilibration of the sulphate-sulphicle pair during water ascent shows that this process would require 220 Myr. Therefore, we conclude that pyrite is formed from precursor Fe monosulphide phases, which rapidly precipitate in the near- surface environment, preserving the isotope fractionation between dissolved sulphate and sulphide established in the deep aquifer. Equilibrium modelling of water-mineral reactions shows slight supersaturation of barite at the discharge temperature. Pyrite is already strongly supersaturated at the temperatures estimated for the aquifer (110degC) and processes in the near-surface environment are most probably related to contact of the thermal water with atmospheric oxygen, resulting in formation of oxidized intermediate sulphur species and precipitation of Fe monosulphide phases, which subsequently recrystallize to pyrite.