Water-rock interaction in the magmatic-hydrothermal system of Nisyros Island (Greece)

In this work, we investigated the water–rock interaction processes taking place in the hydrothermal reservoir of Nisyros through both: (1) a review of the hydrothermal mineralogy encountered in the deep geothermal borehole Nisyros-2; and (2) a comparison of the analytically-derived redox potentials and acidities of fumarolic-related liquids, with those controlled by redox buffers and pH buffers, involving hydrothermal mineral phases. The propylitic zone met in the deep geothermal borehole Nisyros-2, from 950 to 1547 m (total depth), is characterised by abundant, well crystallised epidote, adularia, albite, quartz, pyrite, chlorite, and sericite–muscovite, accompanied by less abundant anhydrite, stilpnomelane, wairakite, garnet, tremolite and pyroxene. These hydrothermal minerals were produced in a comparatively wide temperature range, from 230 to 300 °C, approximately. Hydrothermal assemblages are well developed from 950 to 1360 m, whereas they are less developed below this depth, probably due to low permeability. Based on the RH values calculated for fumarolic gases and for the deep geothermal fluids of Nisyros-1 and Nisyros-2 wells, redox equilibrium with the (FeO)/(FeO1.5) rock buffer appears to be closely attained throughout the hydrothermal reservoir of Nisyros. This conclusion may be easily reconciled with the nearly ubiquitous occurrence of anhydrite and pyrite, since RH values controlled by coexistence of anhydrite and pyrite can be achieved by gas separation. The pH of the liquids feeding the fumarolic vents of Stephanos and Polybote Micros craters was computed, by means of the EQ3 code, based on the Cl–δD relationship which is constrained by the seawater–magmatic water mixing occurring at depth in the hydrothermal–magmatic system of Nisyros. The temperature dependence of analytically-derived pH values for the reservoir liquids feeding the fumarolic vents of Stephanos and Polybote Micros craters suggests that some unspecified pH buffer fixes the acidity of these reservoir liquids at values of 4.72–4.85 and 4.88–5.23, respectively. Many of these pH values are lower than those expected for the full-equilibrium condition, although they are close to those of the reservoir liquids of Nisyros-1, 5.16, and Nisyros-2, 4.87. It is likely that this excess of acidity-producing species, chiefly CO2, promotes release of Fe(II) and Fe(III) to the reservoir liquids through rock dissolution, permitting the attainment of redox equilibrium with the (FeO)/(FeO1.5) rock buffer, as already suggested by the late Werner Giggenbach.