Improved Description of Organic Matter in Shales by Enhanced Solid Fraction Detection with Low-Field ¹H NMR Relaxometry

Nuclear magnetic resonance (NMR) relaxometry is routinely used to characterize the oil fraction in unconventional shale formations with low-field benchtop NMR hardware. However, organic phases with restricted mobility like kerogen and bitumen are typically not detectable with the standard Carr–Purcell–Meiboom–Gill (CPMG) method on such equipment, with the rapid spin–spin (T₂) signal decay of these solid/viscous components not visible to the measurement. The solid-echo (SE) and mixed-echo (ME) pulse sequences offer an alternative to the CPMG, extending the lifetime of the time-domain signal and allowing the capture of solid hydrogen-containing species. Accordingly, we combine NMR relaxation data generated from the application of the CPMG, SE, and ME experiments to a set of powdered oil- and brine-saturated Eagle Ford shale samples, with the aim of identifying and quantifing both the immobile (kerogen/bitumen) and mobile (oil/brine) components. Two-dimensional relaxometry correlating spin–lattice relation times T₁ to the effective decay times T₂ obtained using CPMG and SE techniques provides more complete information on the immobile phases in the shales, such as solid organic matter and clay-bound water. The three spin–echo techniques have similar efficiencies when detecting signal from mobile and low-viscosity fluids, while significant differences are seen in shale samples containing immobile organics. Overall, the combination of the three spin echo techniques provides an improved description of the solid, viscous, and liquid components in the investigated shales at low magnetic field.