Biogenic gas shales, predominantly microbial in origin, form an important class of organic-rich shale reservoirs with a significant economic potential. Yet large gaps remain in the understanding of ...their gas generation, storage, and transport mechanisms, as previous studies have been largely focused on mature thermogenic shale reservoirs. In this study, the pore structure of 18 Antrim Shale samples was characterized using gas adsorption (CO
2
and N
2
). The results show that most of the Antrim Shale samples are rich in organic matter content (0.58 wt.% to 14.15 wt.%), with highest values found in the Lachine and Norwood members. Samples from the Paxton Member, characterized by lower organic content, have smaller micropore surface area and micropore volume but larger meso-macro pore surface area and volume. The deconvolution results of the pore size distribution from the N
2
adsorption indicate that all of the tested Antrim Shale samples have similar pore groups. Organic matter in the Antrim Shale hosts micro pores instead of meso-macro pores, while clay minerals host both micro and meso-macro pores. Mineral-related pores play a primary role in the total porosity. The biogenic Antrim Shale, therefore, has different pore structures from other well-studied thermogenic gas shales worldwide.
•We showed microstructural and mineralogical alteration of the Middle Bakken after two months of exposure to ScCO2 exposure.•Nanoindentation was employed to confrim the long-term micromechanical ...impact of the sample after exposure to ScCO2.•Lack of understanding of these variations in project planning could lead to potential CO2 leakages and environmental hazards in storing CO2.
Considering the importance of carbon neutrality, UCCUS which is underground carbon capture, utilization, and storage has been widely adopted to mitigate climate change. Studies are being conducted to improve this process, however, there is still a lack of knowledge on the multiscale physicochanical alterations that the storage reservoirs may endure due to the long-term exposure to supercritical CO2 (ScCO2). These changes happen from nano- to macro-scale in mineralogy and pore structures which will impact mechanical and petrophysical attributes of the host rock. Since unconventional shale reservoirs have become the target of CO2-EOR and CO2 storage, it is imperative to understand the long-term impact of these alterations due to ScCO2 exposure. This study coupled experimental and theoretical modeling to investigate continuous nano- to macro-scale changes in mechanical, mineralogical, and structural alterations in the Middle Bakken by exposing samples to ScCO2 for 3, 8, 16, 30 and 60 days. Qualitative analysis of electron micrographs pre and post exposure confirmed certain minerals have evolved while image processing showed a quantitative change in pore structures. Moreover, nanomechanical changes pre and post exposure were inspected via nanoindentation method. Furthermore, we assessed how mineral content was impacted during the exposure using X-ray diffraction analysis. Next, we adopted two rock physics models based on mechanical and mineralogical observations to upscale mechanical properties to the macro scale. Analyses of the results indicate that long-term ScCO2 exposure induces mineral dissolution, precipitation and the development of fractures in the host reservoir. Further, CO2 induced alterations can lead to long-term macro-scale weakening causing a loss in mechanical integrity of the Middle Bakken by decreasing its elastic modulus (DS model = –33 %, MT model = -30 %) and increasing its Poisson’s ratio (DS model = +38 %, MT model = +32 %). Overall, this study can provide new insights for a better design and implementation of UCCUS projects in shale reservoirs, most especially in the Middle Bakken and other similar formations, where a lack of understanding of these variations and project planning could lead to potential CO2 leakages and environmental hazards.
Unconventional reservoirs, such as oil and gas shales, are characterized by diverse and heterogeneous pore systems, and their detailed knowledge is critical for understanding fluid storage and ...transport mechanisms. The Devonian Antrim Shale in the Michigan Basin is an unconventional, primarily biogenic gas accumulation with a technical recoverable resource of 19.9 Tcf. While its general formation properties are known, the details of porosity distribution and pore morphology are lacking. This study provides a comprehensive description of the total porosity, pore size distribution, pore morphology and mineral associations for various members of the Antrim Shale sampled at three locations across the basin, and then investigates the factors controlling porosity distribution and the implications for gas sorption. Results indicate that the black-shale members, the Lachine and Norwood, are characterized by a lower porosity (0.1–2%) compared to the organic-lean members, the Paxton and Upper Antrim (2–7% porosity). Total porosity tends to decrease with the increase in organic content in the Antrim Shale as organic matter, in particular solid bitumen, occludes available pore space between mineral grains in the organic-rich black shale members. Organic matter displays little to no porosity of its own at the SEM resolution, but gas adsorption measurements indicate the presence of micropores (<2 nm), whose amount correlates positively to the total organic content. The Norwood member (TOC values up to 25%) is characterized by the largest share of micropores (up to 37% of the total porosity volume), while the organic-lean Paxton Member (TOC < 6%) has the least amount of microporosity (1–6%). Only the Lachine Member and select Upper Member samples showed larger organic matter pores, visible in the SEM images (∼50–100 nm). Mesopores (2–50 nm) are the dominant pore size group in the Antrim Shale, forming 45% to 76% of the pore space, and most of the pores are interparticle and intraparticle pores in and around clays, quartz, feldspar and pyrite grains. No single mineral component influences the total porosity distribution, but clay content exhibits a weak positive correlation to the meso-macro porosity. As microporosity is known to contribute the most to gas adsorption capacity of unconventional reservoirs, TOC appears to be most important factor controlling both CH4 and CO2 storage potential of the Antrim Shale. The Norwood Member, characterized by the highest TOC and microporosity volume as well as surface area of the micropores, is predicted to have the highest gas adsorption capacity but direct sorption measurements will be needed to confirm that. This study highlights some important differences with previous observations about porosity relationship to organic and mineral components of shale reservoirs, and expands the understanding of shale pore systems in the low-maturity range of organic-rich shales.
•Modified pyrolysis methods are needed to determine Oil-In-Place in liquids-rich rocks.•NMR T1-T2 relaxometry and Multi Heating pyrolysis were used to study HC producibility.•HF-NMR at 22 °C ...underestimates the amount of OIP for certain types of organic-rich LRU.•Any chemically ‘extractable’ hydrocarbons are not necessarily ‘producible’
The geochemical and petrophysical complexity of source-rock reservoirs in liquids-rich unconventional (LRU) plays necessitates the implementation of a more expansive analytical protocol for initial play assessment. In this study, original samples from selected source-rock reservoirs in the USA and the UK were analyzed by 22 MHz nuclear magnetic resonance (HF-NMR) T1-T2 mapping, followed by hydrous pyrolysis, and a modified Rock-Eval pyrolysis method (multi-heating step method-MHS). The above methods were complemented by organic petrography under reflected white and UV light excitation of the original and pyrolyzed samples. The analytical protocol presented attempts to better qualify and quantify different petroleum fractions (mobile, heavy hydrocarbons, viscous, solid bitumen), thus provide valuable and refined information about producibility of target intervals during appraisal. Results show how the hydrocarbon fractions interpreted from peak locations and intensities on NMR T1-T2 maps are in good agreement with those from MHS pyrolysis in terms of hydrocarbon mobility/producibility. Results from HP (Hydrous Pyrolysis) experiments show that an exception to this general agreement between NMR and MHS estimates occurs for the Kimmeridge Blackstone Clay samples, where MHS shows an increase of >90% in producible hydrocarbon yields vs. minimal to no presence of mobile hydrocarbons in NMR T1-T2 maps. This study clarifies the role of pore structure and networks in these discrepancies of producible oil estimates when comparing programmed pyrolysis to NMR-based techniques. This novel, multi-step and multidisciplinary approach provides a more advanced screening protocol for identifying zones of higher oil-in-place (OIP) and predicting fluid mobility prior to drilling or completions.
The gas adsorption hysteresis effects have strong implications for the characterization of the micropore structure, which is one of the most important properties of shales. This study describes one ...of the first investigations of low-pressure CO2 adsorption hysteresis illustrated on the Antrim Shale samples, Michigan Basin. A total of 23 samples were characterized by using a combination of X-Ray diffraction (XRD), Rock-Eval pyrolysis, scanning electron microscope (SEM) imaging and CO2 adsorption. The partial least linear regression (PLS) was employed to study the influence of rock composition on the micropore structures and hysteresis index (HI). The results showed that the micropore parameters (surface area and volume) are positively correlated to the amount of organic matter and clay minerals, and have a negative correlation to non-clay minerals. In the Antrim Shale samples, the CO2 adsorption hysteresis seen under low pressure appears to be controlled mainly by the pore network effect caused by the presence of ink-bottle shaped pores, rather than by the swelling of clays and organic matter.
•The micropore structure of Antrim shale samples is studied by using the CO2 adsorption.•Hysteresis index and statistical data analysis are performed to describe the hysteresis phenomena.•The mechanism of the CO2 adsorption hysteresis under low pressure for Antrim shale samples is revealed.
Pores with sizes ranging from nanometers to micrometers are widely distributed in shale gas and shale oil formations. These pores are the sites for hydrocarbon accumulation and provide the flow paths ...for hydrocarbons during production. The Middle Bakken member is the main production zone of the Bakken Formation in North Dakota. In order to reveal the pore structures of the Middle Bakken, we employed field emission scanning electron microscopy (FE-SEM). After segmentation of the SEM images, we calculated the surface area and shape of the pores using image analysis and then quantified the complexity and heterogeneity of the pore structures by applying both fractal and multifractal analyses. Finally, we employed the fractal permeability model to estimate the permeability of the samples. The results showed that different pore types, such as interparticle and intraparticle pores exist in the Middle Bakken samples. Even under the same scale of the same sample, the pore parameters could be different. Sample 2 has the largest average porosity, followed by Sample 1 and Sample 3. The mean pore size of these samples is less than 31 nm indicating that the pores in Middle Bakken samples are very small. The pore structures in the Middle Bakken exhibited fractal and multifractal behavior. The fractal dimension from the entire size range of pores is the largest compared with the fractal dimension of the subdivided groups. The pore size distribution in Sample 2 is the most heterogeneous.
•Image analysis was applied to quantify the pore size and pore shape distributions of Middle Bakken samples.•Different pore groups with different pore size and pore shape were separated.•Fractal and multifractal methods were employed to characterize the pore structures.•Fractal permeability model and capillary tube model were used for the permeability estimation.
Migraines are the leading cause of disability in the United States, and the use of non-pharmaceutical treatments like osteopathic manipulative treatment (OMT) has shown promise. Despite its ...potential, the lack of mechanistic understanding has hindered widespread adoption. This study aims to investigate the efficacy of OMT in treating acute migraines and unravel its underlying mechanisms of action.
Female rats were subjected to a "two-hit" approach to induce migraine-like pain. This involved bilateral injections of Complete Freund's Adjuvant (CFA) into the trapezius muscle (1st hit) followed by exposure to Umbellulone, a human migraine trigger, on Day 6 post-CFA (2nd hit). Soft tissue and articulatory techniques were applied to the cervical region for acute abortive or repeated prophylactic treatment. Cutaneous allodynia and trigeminal system activation were assessed through behavioral tests and immunohistochemical staining.
Following Umbellulone inhalation, CFA-primed rats exhibited periorbital and hind paw allodynia. Immediate application of OMT after Umbellulone inhalation as an abortive treatment partially alleviated cutaneous allodynia. With OMT applied thrice as a prophylactic measure, complete suppression of tactile hypersensitivity was observed. Prophylactic OMT also prevented the increase of c-fos signals in the trigeminal nucleus caudalis and the elevation of calcitonin gene-related peptide expression in trigeminal ganglia induced by CFA and Umbellulone exposure at 2 h post-inhalation.
These findings provide mechanistic insights into OMT's migraine-relief potential and underscore its viability as a non-pharmacological avenue for managing migraines.
