Analytical protocol for measuring micro-molar quantities of sulfur volatile species in experimental high pressure and temperature fluids

Validating thermodynamic models is essential in experimental geosciences for exploring increasingly complex systems and developing analytical protocols. However, investigating solid–fluid equilibria in mm3-sized experimental capsules pose several challenges, particularly in sulfur-bearing chemical systems. These include maintaining bulk fluid composition and performing quantitative analysis with extremely low amounts of synthesized fluid. We present an innovative methodology for measuring ultra-low amounts of sulfur volatiles (H2S and SO2) generated during experimental runs at high pressure and temperature conditions of 3 GPa and 700°C. Using solid sulfides (FeS + FeS2) and water as reactants, we performed redox-controlled syntheses employing a piston cylinder apparatus. We demonstrate that ex-situ measurements of these fluids by quadrupole mass spectrometry ensure accurate and precise analysis, confirming predicted thermodynamic compositions. This methodology allows in-depht investigation of sulfide solid–fluid equilibria, shedding light on sulfur volatiles behavior and geochemical cycles under high P–T conditions characteristic of the Earth’s interior.