Insights on Using Solid Bitumen Reflectance as a Thermal Maturity Proxy in the Bakken Formation, Williston Basin, USA.

To further refine the use of solid bitumen reflectance (BRo in %) as a measurement of thermal maturity in source-rock reservoirs, we examined its relationship to other thermal proxies in the Bakken Formation. Comparisons included criteria from programmed temperature pyrolysis, gas chromatography (GC), and Fourier transform infrared (FTIR) spectroscopy. Thirty-two organic-rich samples from the lower and upper shale members of the Devonian-Lower Carboniferous Bakken Formation were collected from eight cores across the Williston Basin, USA, at depths (∼7575-11,330 ft) representing immature through post peak oil/early condensate thermal maturity conditions based on proximity to current hydrocarbon production. Unmodified BRo values were correlated to programmed temperature pyrolysis parameters (hydrogen index, production index, and T max), normal hydrocarbon and isoprenoid analysis of extractable organic matter (pristane/n-C17 and phytane/n-C18) from GC analysis, and peak ratios from FTIR spectroscopy (branching ratio and A-factor). Strong correlations between unmodified BRo values (not corrected to a vitrinite reflectance equivalent, VRe) and other thermal proxies suggest that BRo can be used as a direct thermal proxy in marine Paleozoic source-rock reservoirs where vitrinite is rare or absent. Moreover, an apparent overestimation of VRe at the lowest thermal maturity investigated herein may argue against the application of BRo conversion to VRe in the Bakken Formation. Solvent extraction caused a consistent decrease in BRo when average post-extraction values from a given well were compared to BRo prior to extraction, although the decrease in mean value was not statistically significant. These results are discussed in the context of advocating for the use of unmodified BRo values as a best practice for thermal maturity determination in Paleozoic marine source-rock reservoirs.

Cathodoluminescence differentiates sedimentary organic matter types.

High-resolution scanning electron microscopy (SEM) visualization of sedimentary organic matter is widely utilized in the geosciences for evaluating microscale rock properties relevant to depositional environment, diagenesis, and the processes of fluid generation, transport, and storage. However, despite thousands of studies which have incorporated SEM methods, the inability of SEM to differentiate sedimentary organic matter types has hampered the pace of scientific advancement. In this study, we show that SEM-cathodoluminescence (CL) properties can be used to identify and characterize sedimentary organic matter at low thermal maturity conditions. Eleven varied mudstone samples with a broad array of sedimentary organic matter types, ranging from the Paleoproterozoic to Eocene in age, were investigated. Sedimentary organic matter fluorescence intensity and CL intensity showed an almost one-to-one correspondence, with certain exceptions in three samples potentially related to radiolytic alteration. Therefore, because CL emission can be used as a proxy for fluorescence emission from sedimentary organic matter, CL emission during SEM visualization can be used to differentiate fluorescent from non-fluorescent sedimentary organic matter. This result will allow CL to be used as a visual means to quickly differentiate sedimentary organic matter types without employing correlative optical microscopy and could be widely and rapidly adapted for SEM-based studies in the geosciences.

Organic petrographic evaluation of carbonaceous material in sediments of the Kinnickinnic River, Milwaukee, WI, U.S.A.

This study examines the use of organic petrology techniques to quantify the amount of coal and carbonaceous combustion by-products (i.e., coke, coal tar/pitch, cenospheres) in sediments taken from the Kinnickinnic River adjacent to the former site of the Milwaukee Solvay Coke and Gas Company. These materials are of concern as contaminants like polycyclic aromatic hydrocarbons (PAHs) are known to readily adsorb to coal and combustion byproducts. Kinnickinnic River sediment samples (n = 36) ranging in depth (1-11 ft.) were collected from eight core locations to quantify and characterize carbonaceous material in the sediments. To determine the amount (vol%) of organic particulates, U.S. Geological Survey (USGS) modified the existing ASTM D2799 using the following categories: coal, coke, coal tar/pitch, inertinite organics, plant material, cenospheres, and mineral matter. Coal fragments were subdivided by rank using vitrinite reflectance (Ro, %) and organic components were further subdivided into the size fractions of coarse (250-1000 µm), fine (63-250 µm), and very fine (<63 µm). Of the 36 samples analyzed, concentrations of coal, coke, and coal tar/pitch ranged from 0 to 18.2 vol%, 0 to 32.0 vol%, and 0 to 2.6 vol%, respectively, with the highest concentrations occurring near point sources (e.g. discharge pipe and coal unloading operations). Samples that were furthest upstream and downstream from the Solvay site exhibited a marked decrease in particulate organics, with exception of one upstream location which had 19.8 vol% coke. Overall, the modified ASTM method provided a means to quantify the abundance of carbonaceous material present in the sediments. Petrography and total PAH concentrations did not provide a clear correlation to organic matter type or size fraction but the samples with the highest vol% organic matter in each core generally corresponded to the sample with the highest bulk PAH content.

Utilization of integrated correlative light and electron microscopy (iCLEM) for imaging sedimentary organic matter.

We report here a new microscopic technique for imaging and identifying sedimentary organic matter in geologic materials that combines inverted fluorescence microscopy with scanning electron microscopy and allows for sequential imaging of the same region of interest without transferring the sample between instruments. This integrated correlative light and electron microscopy technique is demonstrated with observations from an immature lacustrine oil shale from the Eocene Green River Mahogany Zone and mid-oil window paralic shale from the Upper Cretaceous Tuscaloosa Group. This technique has the potential to allow for identification and characterization of organic matter in shale hydrocarbon reservoirs that is not possible using either light or electron microscopy alone, and may be applied to understanding the organic matter type and thermal regime in which organic nanoporosity forms, thereby reducing uncertainty in the estimation of undiscovered hydrocarbon resources.