Understanding organic matter heterogeneity and maturation rate by Raman spectroscopy

Solid organic matter (OM) in sedimentary rocks produces petroleum and solid bitumen when it undergoes thermal maturation. The solid OM is a 'geomacromolecule', usually representing a mixture of various organisms with distinct biogenic origins, and can have high heterogeneity in composition. Programmed pyrolysis is a common method to reveal bulk geochemical characteristics of the dominant OM, while detailed organic petrography is required to reveal information about the biogenic origin of contributing macerals. Despite the advantages of programmed pyrolysis, it cannot provide information about the heterogeneity of chemical compositions present in the individual OM types. Therefore, other analytical techniques such as Raman spectroscopy are necessary. In this study, we compared geochemical characteristics and Raman spectra of two sets of naturally and artificially matured Bakken source rock samples. A continuous Raman spectral map on solid bitumen particles was created from the artificially matured hydrous pyrolysis residues, in particular, to show the systematic chemical modifications in microscale. Spectroscopic data was plotted for both sets against thermal maturity to compare maturation rate/path for these two separate groups. The outcome showed that artificial maturation through hydrous pyrolysis does not follow the same trend as naturally-matured samples although having similar solid bitumen reflectance values (%SBRo). Furthermore, Raman spectroscopy of solid bitumen from artificially matured samples indicated the heterogeneity of OM decreases as maturity increases. This may represent an alteration in chemical structure towards more uniform compounds at higher maturity. This study may emphasize the necessity of using analytical methods such as Raman spectroscopy along with conventional geochemical methods to better reveal the underlying chemical structure of OM. Finally, observation by Raman spectroscopy of chemical alteration of OM during artificial maturation may assist in the proposal of improved pyrolysis protocols to better resemble natural geologic processes.