Kinetics of pyrite to pyrrhotite reduction by hydrogen in calcite buffered solutions between 90 and 180 °C: Implications for nuclear waste disposal

The kinetics of abiotic redox reactions induced by hydrogen are poorly documented although it represents a growing area of interest in terms of both nuclear waste storage assessment and the comprehensive study of hydrogen-rich fluid in mid-ocean ridge hydrothermal systems. We present an experimental kinetics study of pyrite reduction into pyrrhotite under significant H₂ pressure and mid-hydrothermal conditions. We describe the mechanism and kinetic behavior of this reaction by combining textural and solution analyses under various conditions of temperature, pyrite particles size, H₂ pressure and pH. When pH is controlled by calcite, the reaction presents all the characteristics of a coupled dissolution-precipitation mechanism occurring at the pyrite-pyrrhotite interface. By considering the chemical affinity of the coupled reaction as a function of reaction extent, we demonstrate that the spatial coupling is induced both by pyrite as a substrate for pyrrhotite nucleation and by the role of fluid chemistry at the reaction front. Far from equilibrium with respect to pyrite, the kinetics of sulfide production associated with the reaction are linearly related to the square root of time with an activation energy of 53 kJ/mol. This value is higher than what is expected for a diffusion-controlled kinetic regime. We suggest that the reaction rate is controlled both by pyrite reductive dissolution and by sulfide diffusion through the porous pyrrhotite microstructure. We provide a simple sulfide production-rate expression on the basis of our measured rate constants that can be used in geochemical modeling to further evaluate the impact of hydrogen on pyrite under nuclear waste disposal conditions.