Although carbonyl sulfide (COS) has long been recognized as a potentially valuable geothermometric indicator, its use has been limited by the scarcity of analytical data, mainly due to instrumental limitations in the 1990s. In this work, new geothermometric functions and graphical tools were developed for the H2O–CO2–H2S–H2–CH4–CO–COS system and applied to new data of Larderello (Italy) and Krafla (Iceland) geothermal fluids. Thermodynamic data of COS and other gas species were re-evaluated, vapor–liquid distribution coefficients were extrapolated, and the gas equilibria were formulated for different aquifer conditions: saturated pure liquid water, two-phase liquid plus vapor mixtures produced by addition of equilibrium liquid to equilibrium vapor (liquid gain) – i.e., the approach of Giggenbach (1980), but assigning the pivotal role to steam rather than liquid water –, saturated vapors, saturated vapors affected by removal of equilibrium liquid (steam condensate), and superheated (dry) vapors. The application of the H2O–CO2–H2S–H2–CH4–CO–COS geothermometer enabled us to refine the outcomes obtained by using the graphical tools and functions based on gas equilibria for the H2O–CO2–H2–CH4–CO system. The improved geothermometric results were achieved by accounting for the effects of the reaction COS + H2 = CO +H2S, which likely governs the final re-equilibration of CO and COS due to their low concentrations and the high thermodynamic probability of spontaneous progress under geothermal conditions. Nevertheless, it cannot be ruled out that the concentration of COS in some fluid samples of this study may also be influenced by the reaction COS + H2O = CO2 + H2S. This work demonstrates the analytical and interpretative value of incorporating COS in routine determinations of geothermal gases and underscores the need for further experimental and theoretical studies to better constrain the kinetics and mechanisms of the reaction converting COS and H2 in CO and H2S.
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