Quantitative models of hydrothermal fluid–mineral reaction:The Ischia case

The intricate pathways of fluid–mineral reactions occurring underneath active hydrothermal systems are explored in this study by applying reaction path modelling to the Ischia case study. Ischia Island, in Southern Italy, hosts a well-developed and structurally complex hydrothermal system which, because of its heterogeneity in chemical and physical properties, is an ideal test sites for evaluating potentialities/limitations of quantitative geochemical models of hydrothermal reactions. We used the EQ3/6 software package, version 7.2b, to model reaction of infiltrating waters (mixtures of meteoric water and seawater in variable proportions) with Ischia’s reservoir rocks (the Mount Epomeo Green Tuff units; MEGT). The mineral assemblage and composition of such MEGT units were initially characterised by ad hoc designed optical microscopy and electron microprobe analysis, showing that phenocrysts (dominantly alkali–feldspars and plagioclase) are set in a pervasively altered (with abundant clay minerals and zeolites) groundmass. Reaction of infiltrating waters with MEGT minerals was simulated over a range of realistic (for Ischia) temperatures (95–260° C) and CO2 fugacities (10 ^-0.2 to 10^0.5) bar. During the model runs, a set of secondary minerals (selected based on independent information from alteration minerals’ studies) was allowed to precipitate from model solutions, when saturation was achieved. The compositional evolution of model solutions obtained in the 95–260°C runs were finally compared with compositions of Ischia’s thermal groundwaters, demonstrating an overall agreement. Our simulations, in particular, well reproduce the Mg-depleting maturation path of hydrothermal solutions, and have end-of-run model solutions whose Na–K–Mg compositions well reflect attainment of full-equilibrium conditions at run temperature. High-temperature (180–260° C) model runs are those best matching the Na–K–Mg compositions of Ischia’s most chemically mature water samples, supporting quenching of deep-reservoir conditions for these surface manifestations; whilst Fe, SiO2 and, to a lesser extent, SO4 contents of natural samples are better reproduced in low-temperature (95°C) runs, suggesting that these species reflect conditions of water–rock interaction in the shallow hydrothermal environment. The ability of model runs to reproduce the compositional features of Ischia’s thermal manifestations, demonstrated here, adds supplementary confidence on reaction path modelling as a realistic and insightful representation of mineral–fluid hydrothermal reactions. Our results, in particular, demonstrate the significant impact of host rock minerals’ assemblage in governing the paths and trends of hydrothermal fluids’ maturation.