Megalitres of water with associated dissolved oxygen are injected into shale reservoirs during the hydraulic fracturing process. Pyrite oxidation, if it occurs in-situ, can generate extra H+, thereby dissolving calcite and increasing the salinity of flowback water. The process of calcite dissolution may soften the hydraulic fracture surfaces, resulting in proppants embedment and thus decreasing fracture conductivity for calcite-rich shales. Therefore, it is of vital importance to understand the impact of in-situ pyrite oxidation on fluid-shale interactions, particularly calcite dissolution, to help industry screen and design hydraulic fracturing fluids in shales. Spontaneous imbibition experiments were performed using Marcellus shale samples under three conditions: i) ambient conditions, where the fluid was in equilibrium with atmospheric air throughout the tests, ii) limited O2 condition, where the fluid was free equilibrated with air in a sealed cylinder and iii) vacuum condition, where the fluid in a sealed cylinder was degassed. The pH and ion concentrations were measured upon completion of the experiments. To further explore how pyrite oxidation affects fluid-rock interactions, we performed geochemical simulations with considerations of mineral dissolution (calcite, albite, quartz, chalcopyrite, pyrite and dolomite), surface complexation and the dissolved O2 on fluid salinity.
The spontaneous imbibition tests show that the salinity of fluids in ambient conditions is higher than the limited or vacuumed saturation fluids, confirming that pyrite oxidation generates H+ which would dissolve minerals such as calcite and dolomite. This result is also supported by the observed pH and the concentration of dissolved Ca2+. The fluid fully saturated with O2 has the lowest pH and highest Ca2+ compared to limited O2 saturation condition and degassed condition. Scanning electron microscopy analyses show that brine saturation barely affects the morphology and elemental distribution of pyrite at ambient conditions, suggesting that pyrite oxidation plays a minor role in fluid salinity. Geochemical modelling also indicates that although pyrite oxidation can slightly increase fluid salinity, the salinity increment is less than 5% of reported flowback water salinity, confirming that the dissolved O2 in hydraulic fracturing fluids has a minor effect on fluid-rock interaction thus the salinity increment. This work demonstrates that pyrite dissolution at lab-scale would overestimate the impact of fluid-shale interactions and calcite dissolution in reservoir conditions. We prove that pyrite dissolution in in-situ conditions results in minor implications for fluid-shale interactions and calcite dissolution. Consequently, we limit intrinsic uncertainty of hydraulic fluid design associated with pyrite oxidization especially for calcite-rich shales.