Oxygen isotopic ratios of sulfate ions-water pairs as a possible geothermometer

In this paper a brief review is given of the dependence of the oxygen isotopic fractionation of the sulfate ions-water system on temperature and the pH. From the available experimental data some relationships have been elaborated, which show that the isotopic exchange time is strongly temperature and pH dependent. The times for 97 per cent of isotopic exchange (near equilibrium conditions) at pH 7.0 are about 9 years at 200°C and 0.6 years at 330°C, while at pH 3.8 and at the same temperatures the times of exchange are 1.5 years and 0.08 years respectively. Thus, at the temperatures and pH of geothermal reservoirs the sulfate could be in isotopic equilibrium with environmental water, and the oxygen isotopic fractionation factors of sulfate-water geothermal pairs, being temperature dependent, can be used as geothermometers. Also reported here are some results on the O18 content of sulfate-water pairs from some wells on the edge of and outside the Larderello geothermal basin. The estimated isotopic temperatures are not very significant for the deep reservoir temperatures due to the geological features of the Larderello area which show important outcropping and deep anhydrite layers. Furthermore, as regards the wells outside the Larderello basin (Travale wells) some mixing of the geothermal water with colder underground water has been proved. However, the isotopic temperatures are generally higher than those measured at the well-head, and the highest ones are close to those estimated for the geothermal reservoir. In other geothermal areas more convenient from a geological point of view, the O18 content of the sulfate-water pair can be a useful and accurate thermometer. The O18/O16 ratios of several other sulfates (surface and deep anhydrite samples, sulfate ions in thermal springs) from the same area were also determined and differ substantially from borehole sulfate values.