Nanoscale Molecular Composition of Solid Bitumen from the Eagle Ford Group across a Natural Thermal Maturity Gradient

Microscopic solid bitumen is a petrographically defined secondary organic matter residue produced during petroleum generation and subsequent oil transformation. The presence of solid bitumen impacts many reservoir properties including porosity, permeability, and hydrocarbon generation and storage, among others. Furthermore, solid bitumen reflectance is an important parameter for assessing the thermal maturity of formations with little to no vitrinite. While the molecular composition of solid bitumen will strongly impact associated parameters such as the development of organic matter porosity, hydrocarbon generation, and optical reflectance, assessing the molecular composition of solid bitumen in situ within shale reservoirs can be challenging due to the small grain sizes (often <= 1 mu m in diameter) and the inherent heterogeneity of shale formations. Here we employ the recently developed atomic force microscopy based infrared spectroscopy (AFM-IR) technique to investigate solid bitumen molecular composition in situ within shale samples from the Late Cretaceous Eagle Ford Group. These samples possess sulfur-rich type II kerogens that span a natural thermal maturity gradient from early oil generation to the dry gas window. The application of AFM-IR allows for the rapid collection of thousands of compositional measurements from solid bitumen with similar to 50 nm resolution. Our results indicate that (i) solid bitumen from the lower Eagle Ford displays both intra- and intergranular variation in the relative abundance of CH2, C=C, and C=0 moieties present; (ii) this molecular variation tends to, but does not always, decrease with an increase in thermal maturity; and (iii) the solid bitumen composition between samples, from an atomic ratio perspective, is more similar than analysis of bulk kerogen isolates would indicate. These findings are discussed with perspective toward understanding the impact of thermal stress on the composition of secondary organic matter within the Eagle Ford Shale and highlight the growing awareness that organic matter heterogeneity within petroliferous mudrocks extends down to the nanoscale regime.