Knowledge of water/rock interactions on the surface of fractures is important to develop an understanding of the geological structures and changes within the formation, and to determine hydraulic-fracturing (HF) performance. To obtain this knowledge, this study investigates water/shale interactions in carbonate-rich (Eagle Ford), organic-rich (Green River), clay-rich (Barnett), and other-minerals-rich (Marcellus) shale samples.

Crushed shale samples were exposed to water for 3 weeks at reservoir conditions. The water and rock samples before and after each static experiment were subjected to several analyses. The change in the rock mineralogy was defined by X-ray diffraction (XRD), the elemental composition of rock was determined by X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy energy dispersive spectroscopy (SEM-EDS), and the organic content of rock samples was estimated by thermogravimetric analysis (TGA). The water was analyzed for its anions and cations, total dissolved solids (TDS), conductivity, pH, total organic carbon (TOC), and average particle sizes of colloids. The stability of the colloids was characterized by zeta-potential.

We show that Barnett rock is high in illite content, and the greatest calcite concentration is determined for Eagle Ford. The sulfate content of water correlates with the atomic percent of the sulfur and oxygen elements determined through XPS analyses. The magnesium content of water correlates mainly with the illite amount in the rock, and calcium concentration associates with the calcite and gypsum content of the rock samples. The greatest dissolution rate belongs to the minerals that yield sulfate in the water; then, gypsum and calcite that yield calcium cation in the water come second; and the lowest dissolution rates are obtained from the magnesium-containing minerals (mainly, dolomite). TDS of the water samples shows that Green River has the least tendency to interact with water, and Barnett has the greatest tendency. Zeta-potential values indicate that particles in the water that interacted with Eagle Ford have the highest tendency for precipitation.

The results of this study are used to make suggestions on the engineering of hydraulic-fracturing fluids (HFFs) in the context of water/rock interactions by considering the type and the concentration of ions along with colloidal stability determined through zeta-potential measurements.

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