High microscale variability in Raman thermal maturity estimates from shale organic matter

Raman spectroscopy has recently received attention as a means to estimate thermal maturity of organic matter in petroleum generating source rocks to complement more traditional approaches such as vitrinite reflectance and programmed pyrolysis. While many studies have observed positive correlations between source rock thermal maturity and Raman spectral parameters, little attention has been given to the degree of variation in the Raman response across individual organic grains, especially for shales or mudrocks with highly dispersed organic matter. Here the spatial variation in Raman estimates of thermal maturity within individual organic grains is assessed from shales from the Boquillas, Marcellus, Niobrara, and Woodford Formations. The thermal maturity parameters extracted from Raman spectra can vary widely across distances of ≤5 μm within the same organic grain. These results illustrate the high degree of chemical heterogeneity inherent to the organic matter within these source rocks. Additionally, the spatial pattern of the Raman parameters, as revealed by 2D Raman mapping, imply that organic matter structure is influenced by associations with mineral surfaces within the surrounding rock matrix. Chemical heterogeneity and matrix effects directly impact the Raman response from these types of materials and thus the extracted thermal maturity estimate. These findings highlight the care which must be adopted when making Raman measurements of organic matter within source rock matrices, especially for samples which feature highly dispersed, heterogeneous organic matter as found in petroliferous mudrocks.