Rapid Marcasite to Pyrite Transformation in Acidic Low-Temperature Hydrothermal Fluids and Saturation Index Control on FeS₂ Precipitation Dynamics and Phase Selection

Pyrite is the most abundant metal sulfide in the Earth’s crust and is also found on Mars. It can form by direct hydrothermal precipitation or by polymorphic phase transformation from marcasite. However, the control on the dynamics of hydrothermal pyrite precipitation is poorly understood, and the kinetics of the hydrothermal transformation from marcasite to pyrite is unknown. To address these issues, we quantified pyrite and marcasite formation in hydrothermal fluids at pH 1, using pyrrhotite as a precursor mineral to produce supersaturated solutions. In situ powder X-ray diffraction experiments at 190 °C showed that hydrothermal fluids rich in ΣS­(-II) (0.2 molal) favored the precipitation of nanocrystal pyrite (∼20 nm) due to a high saturation index (>105), while ΣS­(-II)-free fluids produced a mixture of marcasite and pyrite nanocrystals (21–46 nm) due to a low saturation index (4). The fluid/rock ratio (70 and 120 g/g at 210 °C) can also affect the saturation indices of these fluids, influencing nucleation and crystal growth dynamics of pyrite and marcasite and resulting in complex evolution of crystallite size, phase abundance, and the pyrite/marcasite ratio. Ex situ hydrothermal experiments at 210 °C showed rapid transformation from marcasite to pyrite, with around 95% marcasite being transformed to pyrite in 20 weeks, compared to more than 6.3 million years at 210 °C under dry conditions based on extrapolation from previous kinetic studies. These results suggest that saturation index influences hydrothermal precipitation dynamics and controls phase selection between pyrite and marcasite and that marcasite may not survive over geological time in low-temperature (