Stability and abundance of the trisulfur radical ion S3- in hydrothermal fluids

Abstract

The interpretation of sulfur behavior in geological fluids and melts is based on a long-standing paradigm that sulfate, sulfide, and sulfur dioxide are the major sulfur compounds. This paradigm was recently challenged by the discovery of the trisulfur ion S3- in aqueous S-bearing fluids from laboratory experiments at elevated temperatures. However, the stability and abundance of this potentially important sulfur species remain insufficiently quantified at hydrothermal conditions. Here we used in situ Raman spectroscopy on model thiosulfate, sulfide, and sulfate aqueous solutions across a wide range of sulfur concentration (0.5-10.0 wt%), acidity (pH 3-8), temperature (200-500 °C), and pressure (15-1500 bar) to identify the different sulfur species and determine their concentrations. Results show that in the low-density (<0.2g/cm3) vapor phase, H2S is the only detectable sulfur form. By contrast, in the denser liquid and supercritical fluid phase, together with sulfide and sulfate, the trisulfur radical ion S3- is a ubiquitous and thermodynamically stable species from 200 °C to at least 500 °C. In addition, the disulfur radical ion S2- is detected at 450-500 °C in most solutions, and polymeric molecular sulfur with a maximum abundance around 300 °C in S-rich solutions. These results, combined with revised literature data, allow the thermodynamic properties of S3- to be constrained, enabling quantitative predictions of its abundance over a wide temperature and pressure range of crustal fluids. These predictions suggest that S3- may account for up to 10% of total dissolved sulfur (Stot) at 300-500 °C in fluids from arc-related magmatic-hydrothermal systems, and more than 50% Stot at 600-700 °C in S-rich fluids produced via prograde metamorphism of pyrite-bearing rocks. The trisulfur ion may favor the mobility of sulfur itself and associated metals (Au, Cu, Pt, Mo) in geological fluids over a large range of depth and provide the source of these elements for orogenic Au and porphyry-epithermal Cu-Au-Mo deposits. Furthermore, the ubiquity of S3- in aqueous sulfate-sulfide systems offers new interpretations of the kinetics and mechanisms of sulfur redox reactions at elevated temperatures and associated mass-dependent and mass-independent fractionation of sulfur isotopes.