Reactive fluid flow guided by grain-scale equilibrium reactions during eclogitization of dry crustal rocks

Abstract

AbstractFluid flow in crystalline rocks in the absence of fractures or ductile shear zones dominantly occurs by grain boundary diffusion, as it is faster than volume diffusion. It is, however, unclear how reactive fluid flow is guided through such pathways. We present a microstructural, mineral chemical, and thermodynamic analysis of a static fluid-driven reaction from dry granulite to ‘wet’ eclogite. Fluid infiltration resulted in re-equilibration at eclogite-facies conditions, indicating that the granulitic protolith was out of equilibrium, but unable to adjust to changing P–T conditions. The transformation occurred in three steps: (1) initial hydration along plagioclase grain boundaries, (2) complete breakdown of plagioclase and hydration along phase boundaries between plagioclase and garnet/clinopyroxene, and (3) re-equilibration of the rock to an eclogite-facies mineral assemblage. Thermodynamic modelling of local compositions reveals that this reaction sequence is proportional to the local decrease of the Gibbs free energy calculated for ‘dry’ and ‘wet’ cases. These energy differences result in increased net reaction rates and the reactions that result in the largest decrease of the Gibbs free energy occur first. In addition, these reactions result in a local volume decrease leading to porosity formation; i.e., pathways for new fluid to enter the reaction site thus controlling net fluid flow. Element transport to and from the reaction sites only occurs if it is energetically beneficial, and enough transport agent is available. Reactive fluid flow during static re-equilibration of nominally impermeable rocks is thus guided by differences in the energy budget of the local equilibrium domains.