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At least 73 records · Page 4

Strain-Based Assessment of Shale Caprock during Cyclic Underground Hydrogen Storage

Successful large-scale underground hydrogen storage (UHS) in depleted gas reservoirs depends on the integrity of the overlying caprock to prevent hydrogen loss during cyclic injection and depletion. Prior studies on crushed Marcellus shale, a potential caprock, indicate that cyclic hydrogen injection and depletion induces microstructural changes, increasing porosity and permeability. However, the extent of these changes in intact shale remains unclear. This study presents a strain-based experimental approach to quantify volumetric strain evolution in intact Marcellus shale matrix under unconstrained stress conditions. A quadrant-shaped shale sample without visible fractures underwent eight hydrostatic pore-pressure cycles (injection to 1500 psi and depletion to 500 psi in 250 psi steps). Linear strain gauges measured strain in three orthogonal directions. Results indicate progressive plastic strain accumulation, leading to an ∼12% increase in matrix porosity after eight cycles, with an estimated 19% increase after 30 cycles. This porosity increase follows a logarithmic trend, suggesting a diminishing effect in later cycles. Additionally, permeability and diffusive mass flux are projected to rise by ∼70% over 30 cycles, enhancing hydrogen migration risk. The shale matrix also exhibited mechanical stiffening over successive cycles, limiting large-scale deformation but not preventing porosity enhancement. A new parameter, α, was introduced to characterize shale sensitivity to cyclic loading, aiding UHS caprock assessments. These findings underscore the necessity of incorporating cyclic loading effects in UHS site selection and operational strategies to ensure long-term storage integrity.

08 HYDROGEN↗

Tuscaloosa Marine Shale Laboratory

The Tuscaloosa Marine Shale (TMS) in Louisiana and Mississippi is an Upper Cretaceous source rock formation sandwiched between the sands of the upper and lower Tuscaloosa sections. The TMS is believed to be the source rock for underlying prolific Tuscaloosa sand formation. The TMS has an unproven estimate of 7,000,000,000 bbls of recoverable oil while its current total average production is about 3,000 bbls of oil per day in 2017. In 2013 and 2014, more than 80 wells were drilled horizontally into the TMS that were fractured using multi-stage fracturing technology. The results from this have been mixed, but recent production for several wells show an appealing initial oil production rate of more than 1000 bbl/day. The preliminary core analysis by industry partners and a few literature studies shows that the TMS is one of the most clay-rich and sensitive shales to water. Due to these and other technical problems, there is high risk for the economic development of TMS compared to other shale plays. The experiences of major industrial players in the TMS show the necessity of open and collaborative efforts to better understand the critical gaps in the development of this challenging and potentially highly economic shale play to enable more cost-efficient and environmentally-sound recovery from this unconventional liquid-rich shale play. The overall objective of this project is to form a consortium of science and industry partners to address the following six major objectives using scientific and technical approaches: 1. To improve wellbore integrity by better understanding the sources of the wellbore instability issues, proposing innovative mud and cement design for the TMS. 2. To improve formation evaluation using laboratory techniques for the evaluation of mineralogical composition, organic content, and produced-water chemistry as well as well log and geophysical analysis. 3. To determine the role of geologic discontinuities on fracture growth and shale creep behavior using digital image correlation technique. 4. To investigate the application of stable CO 2 foam and super-hydrophobic proppants for improved reservoir stimulation. 5. To better understand the nature of water/hydrocarbon/CO 2 flow in clay and organic-rich formation and the role of water/fluid interaction on recovery. 6. To prepare better socio-economic environment for TMS development by community engagement. Subsequently, the TMS virtual laboratory conducted testing and analysis of various properties of rock and formation fluids from the TMS, including but not limited to the following: Analyzing reports and logs to better understand the source of wellbore instability in TMS wells; Experiments to design a customized cement based on TMS requirements; Experiments to obtain the mineralogical and geochemical composition of TMS samples; Seismic analysis of TMS geophysical data to better predict total organic carbon (TOC) content and brittleness in TMS; Well log analysis to better estimate the TOC and geo-mechanical properties of TMS; Experiments on formation water to understand the chemistry of produced water; Experiments to determine the role of lamination and natural fractures on fracture propagation or rock deformation using digital image correlation technique in in-direct tensile tests, semi-circular bend test and creep tests Experiments to determine the stability and rheological properties of nanoparticle-stabilized CO 2 foam in TMS rock samples; Experiments to determine fluid dynamics in un-propped TMS fractures and the role of nano-coating of proppants on fluid dynamics in fractures with proppants; Micro-fluidics experiments to enhance the understanding of fluid dynamics in tight liquidrich pores with high clay content; Socio-economic studies to better engage communities in TMS development.

58 GEOSCIENCES↗

Multiple experimental studies of pore structure and mineral grain sizes of the Woodford shale in southern Oklahoma, USA

Pore structure study is an important part of unconventional shale reservoir characterization, since the pore system provides the primary petroleum storage space and fluid flow pathways. Previous studies have suggested that the pore structure is related to the total organic carbon (TOC) content, mineral compositions, and the maturity of the organic matter (OM). However, few studies have focused on the mineral grains, the primary grains being deposited but before cementation, which are the building blocks of shale. Eight Woodford Shale outcrop samples from southern Oklahoma were chosen to study the effects of mineral grain size on the pore structure characterization, using multiple and complementary experimental approaches, including laser diffraction, mineralogy, TOC, pyrolysis, liquid immersion porosimetry, mercury intrusion porosimetry, gas physisorption, (ultra) small angle X-ray scattering, scanning electron microscopy, and spontaneous imbibition. The results from different experiments of eight samples show that the Woodford Shale has the mean mineral grain diameters at 3–6 μm, a wide range of porosity at 3–40% and pore diameters at 50–1,000 nm, and various pore connectivity. Grain size variation was probably caused by the sea-level fluctuation during its deposition, which affect the porosity, pore size distribution, and pore connectivity. With decreasing mineral grain sizes, the porosity tends to increase while the pore connectivity worsens. The results also indicate that OM and carbonates in this low-maturity Woodford Shale could block the pores and decrease the porosity. Coupling with the grain size analyses, the control of depositional environment on grain sizes and subsequent effects on pore structure is identified. The pore structure characteristics over a wide pore-diameter range provided by multiple experiments could improve the understanding of storage space and fluid flow in the Woodford Shale to further increase its petroleum production.

54 ENVIRONMENTAL SCIENCES↗

Coupled Transport, Reactivity, and Mechanics in Fractured Shale Caprocks

Abstract Shales are low‐permeability caprocks that confine fluid, such as CO 2 , nuclear waste, and hydrogen, in storage formations. Stress‐induced fractures in shale caprocks provide pathways for fluid to leak and potentially contaminate fresh water aquifers. Fractured shales are also increasingly considered as resources for CO 2 sequestration, enhanced geothermal, and unconventional energy recovery. Injecting reactive fluids into shales introduces chemical disequilibrium, causing an onset of a series of dissolution, precipitation, and fines mobilization mechanisms. The reactions have rapid kinetics and significant impact on porosity and permeability; consequently, flow and storage properties of caprocks. While previous research has explored the separate effects of these reactions, this study aims to uncover their simultaneous occurrence and collective influence. This study unveils these highly coupled transport and reactivity mechanisms by tracking and visualizing the reaction‐induced alterations in the matrix, microcracks, and fractures of shales over time. We conducted brine injection experiments sequentially at pH 4 and 2 in a naturally fractured Wolfcamp shale sample while simultaneously imaging the dynamic processes using X‐ray computed tomography (CT). CT images are validated by finer resolution images obtained using micro‐CT and scanning electron microscopy. We also tracked the sample permeability and fluid chemistry using brine permeability and inductively coupled plasma mass spectrometry, respectively. Findings show that fluid primarily flowed through fractures, dissolving reactive minerals and mobilizing fines on fracture surfaces. Dissolution of fracture asperities under confining stress resulted in the closing of fractures. Clogging in narrow fracture pathways, caused by fines accumulation, diverted fluid flow into matrix pores.

58 GEOSCIENCES↗

AmeriFlux FLUXNET-1F US-SSH Susquehanna Shale Hills Critical Zone Observatory

This is the AmeriFlux Management Project (AMP) created FLUXNET-1F version of the carbon flux data for the site US-SSH Susquehanna Shale Hills Critical Zone Observatory. This is the FLUXNET version of the carbon flux data for the site US-SSH Susquehanna Shale Hills Critical Zone Observatory produced by applying the standard ONEFlux (1F) software. Site Description - The Susquehanna Shale Hills Critical Zone Observatory is comprised of one first-order catchment in the Susquehanna River basin. This catchment, known as Shale Hills, is about 8 hectares in total area. The stream that defines the Shale Hills catchment flows into Shavers Creek in the Juniata River sub-basin. The vegetation cover at Shale Hills is dominated by deciduous broadleaf forest, with some evergreen needleleaf trees along the stream.

Forsythe, Brandon R.↗

Influence of sequential stimulation practices on geochemical alteration of shale

Water-based hydraulic fracturing fluids (HFFs) can chemically interact with formation shale, resulting in altered porosity and permeability of the host rock. Experimental investigations of spatial and temporal shale-HFF interactions are helpful in interpreting chemical compositions of the injectate, as well as predicting alteration of hydraulic properties in the reservoir due to mineral dissolution and precipitation. Most bench-top experiments designed to study shale-HFF chemical interactions, either using batch reactors or flow-through setups, are carried out assuming that the acid spearhead has already become mixed with neutral HFFs. During operations, however, HFFs are typically injected according to a sequenced pumping schedule, starting with a concentrated acid spearhead, followed by multiple additions of near-neutral pH HFFs containing chemical amendments and proppant. In this study, we use geochemical modeling to consider whether this pre-mixed experimental protocol provides results directly comparable to a sequential discrete fluid-shale interaction protocol. Our results show that for the batch system, the transient evolution in major ion concentrations is faster with the sequential procedure. After 2 h of reaction time, the two protocols converge to the same aqueous concentrations. In a flow-through geometry, the pre-mixed model predicts extensive chemical alteration close to the injection point but negligible alteration downstream. In contrast, the sequential model predicts mineral reactions over hundreds of meters along the flow path. The extent of shale alteration in the sequential model at a given location depends on shale mineralogy and where the acid spearhead resides during the shut-in period. The predictive model developed in this study can help experimentalists to design bench-top tests and operators to better translate the results of laboratory experiments into practical applications.

Li, Qingyun↗

Produced Fluid Induced Mineralogy and Elemental Alterations of Caney Shale, Southern Oklahoma

ABSTRACT This study involves batch reactor experiments and subsequent analyses of samples from Caney Shale in the Ardmore Basin of South-Central Oklahoma. Samples include mainly rock cores and cuttings recovered from two wells respectively drilled vertically through and horizontally across the Caney Shale. Mineralogical compositions are obtained by X-Ray Diffraction (XRD) measurements whilst microstructure and elemental distribution are acquired by Scanning Electron Microscopy/Energy Dispersive Spectroscopy (SEM/EDS) respectively. Batch experiments are then conducted using selected rock samples and produced fluid from the Caney Formation. Deionized water is also reacted with some samples to serve as standard. Experiments are conducted at 95°C and ambient pressure for 7 and 30 days to assess the geochemical rock-fluid interactions. Results show rock mineralogical compositions are predominantly quartz, feldspar, carbonates, and clay with minor pyrite. Post-experimental mineralogical changes observed in samples include increased amorphous entities especially within the clay portions of XRD plots and dissolution of feldspar and carbonate minerals and formation of new mineral phases, mostly clays and salts. These are corroborated by EDS elemental analyses which show decreased elemental compositions. The implications of reactions mentioned above include but not limited to, scale formation, clay fines migration and shale softening all of which pose significant permeability impairment on formation over time. INTRODUCTION Shale reservoirs account for a large share of unconventional reservoirs in the world (Lyu et al., 2015). However, ultra-low permeability and high clay compositions pose significant challenges when producing from these reservoirs (Dawuda and Srinivasan, 2022, 2023). Producing from these reservoirs therefore requires horizontal drilling and hydraulic fracturing technologies which have proven their efficacy in generating substantial permeability in reservoirs to ensure production (Fujian et al., 2019; Liu et al., 2018). Even after expensive horizontal drilling and hydraulic fracturing, geochemical reactions between engineered fluids and formation leads to fracture constriction and adversely impact petrophysical properties (permeability and porosity) of the reservoir. These technologies are therefore under constant development and improvement in various aspects to ensure fine tuning for specific reservoirs. Under present conditions, much of the hydrocarbon reserves in unconventional shale reservoirs are left unproduced due to rapid decline in permeability following resumption to production after hydraulic fracturing. It is therefore essential to understand the range of geochemical reactions that cause rapid depletion of permeability after hydraulic fracturing and apply these to each shale reservoir to ensure substantial recovery rates.

Awejori, G. A.↗

Effects of Interactions Between Produced Formation Fluid and Rock Matrix on Pore Structure of Caney Shale, Southern Oklahoma

ABSTRACT: Rock-fluid interactions change properties of shales during exploitation. To investigate effects of rock-fluid interactions on pore structure of shales matrix after hydraulic fracturing, powder samples from two late Mississippian Caney Shale cores in the Ardmore Basin, southern Oklahoma, were used to react with formation produced fluid from the field in the batch reactor analysis. X-ray diffraction for mineralogy and Low-pressure nitrogen adsorption isotherms for pore structure were measured for original, after-7days, and after-30days samples. Results show that the samples consist mainly of quartz, followed by clay minerals, carbonates, and feldspar. The pore sizes of micropore (<2 nm) and mesopore (2-50 nm) increase 14%-233% due to dissolution of pyrite, feldspar, and carbonates after 7 days. Due to the transformation from smectite to illite and the increase of pore size, the specific surface area (SSA) decreases after 7-days interactions. After 30-days interactions, the micropore volume slightly increases and the mesopore and macropore volume decreases. Due to the decrease of pore size, the SSA of 30-days reacted samples increases correspondingly and is lower (for the clay-rich sample) or higher (for the calcareous sample) than that of the unreacted samples. Findings improve our understanding of dynamic alteration of shale properties during production. 1. INTRODUCTION Energy demand will continuously grow owing to the increasing global population as well as energy consumption (EIA, 2023). On the other hand, shale gas and oil reshaped the energy market in the United States, enabling the United States to become a net-export of natural gas country in 2017 (EIA, 2023). However, shale reservoirs are challenging tight formations that are still poorly understood in the extraction and production of hydrocarbons (Ross and Bustin, 2009; Curtis et al., 2012; Xiong et al., 2015, 2021a; Li Y. et al., 2016; Gong et al., 2019a; Benge et al., 2021; Awejori et al., 2022; Huang et al., 2022). One of the most challenging topics is the rock-fluid interactions post hydraulic fracturing and its subsequent impacts on the pore structures of fractured formation matrix.

Xiong, Fengyang↗

Solar heated oil shale pyrolysis process

An improved system for recovery of a liquid hydrocarbon fuel from oil shale is presented. The oil shale pyrolysis system is composed of a retort reactor for receiving a bed of oil shale particules which are heated to pyrolyis temperature by means of a recycled solar heated gas stream. The gas stream is separated from the recovered shale oil and a portion of the gas stream is rapidly heated to pyrolysis temperature by passing it through an efficient solar heater. Steam, oxygen, air or other oxidizing gases can be injected into the recycle gas before or after the recycle gas is heated to pyrolysis temperature and thus raise the temperature before it enters the retort reactor. The use of solar thermal heat to preheat the recycle gas and optionally the steam before introducing it into the bed of shale, increases the yield of shale oil.

Qader, S. A.↗

Hydrogen (H) Isotope Composition of Type II Kerogen Extracted by Pyrolysis-GC-MS-IRMS: Terrestrial Shale Deposits as Martian Analogs

Described here is a technique for H isotope analysis of organic compounds pyrolyzed from kerogens isolated from gas‐ and liquids‐rich shales. Application of this technique will progress the understanding of the use of H isotopes not only in potential kerogen occurrences on Mars, but also in terrestrial oil and gas resource plays. H isotope extraction and analyses were carried out utilizing a CDS 5000 Pyroprobe connected to a Thermo Trace GC interfaced with a Thermo MAT 253 IRMS. Also, a split of GC‐separated products was sent to a DSQ II quadrupole MS to make qualitative and semi‐quantitative compositional measurements of these products. Kerogen samples from five different basins (type II and II‐S) were dehydrated (heated to 80 C overnight under vacuum) and analyzed for their H isotope compositions by Pyrolysis‐GC‐MS‐TC‐IRMS. This technique takes pyrolysis products separated via GC and reacts them in a high temperature conversion furnace (1450 C), which quantitatively forms H2. Samples ranging from ~0.5 to 1.0mg in size, were pyrolyzed at 800 C for 30s. and separated on a Poraplot Q GC column. H isotope data from all kerogen samples typically show enrichment in D from low to high molecular weight. H2O average delta D = ‐215.2 per mille (V‐SMOW), ranging from ‐ 271.8 per mille for the Marcellus Shale to ‐51.9 per mille for a Polish shale. Higher molecular weight compounds like toluene (C7H8) have an average delta D of ‐89.7 per mille, ranging from ‐156.0 per mille for the Barnett Shale to ‐50.0 per mille for the Monterey Shale. We interpret these data as representative of potential H isotope exchange between hydrocarbons and sediment pore water during basin formation. Since hydrocarbon H isotopes readily exchange with water, these data may provide some useful information on gas‐water or oil‐water interaction in resource plays, and further as a possible indicator of paleoenvironmental conditions. Alternatively, our data may be an indication of H isotope exchange with water and/or acid during the kerogen isolation process. Either of these interpretations will prove useful when deciphering H isotope data derived from kerogen analyses. Understanding the role that these H‐bearing compounds play in terrestrial shale paleo‐environmental reconstruction may also prove useful as analogs for understanding the interactions of water and potential kerogen/organic compounds on the planet Mars.

Socki, Richard A.↗

Experimental and numerical investigation of proppant embedment and conductivity reduction within a fracture in the Caney Shale, Southern Oklahoma, USA

The current worldwide energy supply is insufficient to meet the rising demand. As a result, the energy prices are expected to keep soaring despite the recent increases in a variety of renewable energy resources. Although not renewable, shale oil and gas — “unconventional” hydrocarbon resources are relatively clean forms of energy resources, which still hold a vast share of the energy market. For many oil and gas companies, meeting profitable production goals from shale reservoirs is sometimes challenging, due to the loss of fracture conductivity and premature declines in the production. In this paper we investigate the stress-dependent changes in the hydraulic conductivity of proppant-filled fractures and mechanical fracture–proppant interactions in Caney Shale, a calcareous, organic-rich mudrock, through laboratory experiments and numerical modeling. American Petroleum Institute (API) fracture conductivity tests were conducted using 2% KCl on five locations within the Caney Shale that consisted of selecting three brittle (reservoir) zones and two ductile zones. Confining pressures ranged from 1,000 psi to 12,000 psi at 210 °F. Conductivity, permeability as well as embedment were measured during the test. Also, an additional, laboratory in-situ visualization test was conducted to examine the detailed proppant-shale matrix interaction under elevated stress (3,920 psi effective stress) and temperature (252 °F), with a synthetic reservoir fluid. Our experimental results have confirmed that improved fracture conductivity is attributed to proppant size, and that the increase in porosity of the proppant pack, closure pressure changes and the reduction in fracture conductivity are a function of many factors such as fracture closure stress.

04 OIL SHALES AND TAR SANDS↗

Small-Angle Neutron Scattering Investigation of Oil Recovery in Mineralogically Distinct Wolfcamp Shale Strata

Understanding and improving hydrocarbon yields during enhanced oil recovery (EOR) in unconventional reservoirs is complicated by the intrinsic mineralogical and geochemical heterogeneity of shale formations. Here, in this study, we utilized small-angle neutron scattering (SANS) and ultra-small-angle neutron scattering (USANS) to investigate the degree of oil retention and its location in the nanoporous shale matrix for two mineralogically distinct shale samples. The two samples, dubbed “dark” and “light” based on their color, were taken from adjacent strata in a Wolfcamp shale core. While both samples contained kerogen, the dark sample contained more kerogen and clay (43.7 wt %) while the light sample contained more calcite (54.9 wt %). Samples were presaturated with decane, a model hydrocarbon, prior to pressure cycling with methane. Results showed significantly more retention of decane in 1.5–10 nm radius pores of both, likely indicating that oil is retained within kerogen nanopores. Although the dark sample had a higher porosity of 8.7%, versus 3.3% for the light sample, more pores were accessible to decane and a higher percentage of the imbibed decane was removable from the light sample compared to the dark sample. The majority of decane was not recoverable for the dark sample, indicating that EOR with methane can be challenging. These new findings can help to model expected recoveries of in-place oil from heterogeneous shale formations, as well as inform improved EOR strategies.

04 OIL SHALES AND TAR SANDS↗

Aromatic amino acid metabolism and active transport regulation are implicated in microbial persistence in fractured shale reservoirs

Abstract Hydraulic fracturing has unlocked vast amounts of hydrocarbons trapped within unconventional shale formations. This large-scale engineering approach inadvertently introduces microorganisms into the hydrocarbon reservoir, allowing them to inhabit a new physical space and thrive in the unique biogeochemical resources present in the environment. Advancing our fundamental understanding of microbial growth and physiology in this extreme subsurface environment is critical to improving biofouling control efficacy and maximizing opportunities for beneficial natural resource exploitation. Here, we used metaproteomics and exometabolomics to investigate the biochemical mechanisms underpinning the adaptation of model bacterium Halanaerobium congolense WG10 and mixed microbial consortia enriched from shale-produced fluids to hypersalinity and very low reservoir flow rates (metabolic stress). We also queried the metabolic foundation for biofilm formation in this system, a major impediment to subsurface energy exploration. For the first time, we report that H. congolense WG10 accumulates tyrosine for osmoprotection, an indication of the flexible robustness of stress tolerance that enables its long-term persistence in fractured shale environments. We also identified aromatic amino acid synthesis and cell wall maintenance as critical to biofilm formation. Finally, regulation of transmembrane transport is key to metabolic stress adaptation in shale bacteria under very low well flow rates. These results provide unique insights that enable better management of hydraulically fractured shale systems, for more efficient and sustainable energy extraction.

04 OIL SHALES AND TAR SANDS↗

Water-Oil Displacement in Shale: New Insights from a Comparative Study Integrating Imbibition Tests and Multiscale Imaging

Water-oil displacement is an important process that occurs in a shale matrix after hydraulic fracturing and in water-based enhanced oil recovery. Current understanding of this displacement process is limited because of the complicated pore structure and surface properties in shale. In this work, this process and its controlling factors are investigated through a comparative study of three shale samples that have different types of pore systems and wettability. Here, an integrated method of imbibition and multiscale imaging was applied, and a modified oleic tracer that can better represent oil flow was used in imbibition testing and micro-computed tomography (CT) imaging. Scanning electron microscope (SEM) pore characterization was then performed under high magnification with guidance from the micro-CT images showing the changes caused by oil or water imbibition. New insights were obtained on the importance of both wettability and pore size effect on oil recovery and the distribution of residual oil after water-oil displacement. Connectivity of pores with different wettability is also discussed based on 3D analysis and SEM pore characterization. Collectively, these new findings improve the understanding of the complicated process of water-oil displacement and the role of influencing factors. Important implications for improved oil recovery strategy in shale are discussed for different types of reservoir rocks. The integrated imaging and imbibition technique provides a new path for further investigation of improved oil recovery in shale.

04 OIL SHALES AND TAR SANDS↗

A new approach to study adsorption on shales and other microporous solids via the thermogravimetric analysis (TGA) technique

Measuring the adsorption of gases in microporous solids like the shales requires accurate knowledge of the solid’s skeletal volume. Helium (He) is commonly used to determine the sample’s skeletal volume based on the assumption that it does not adsorb in these porous media. The validity of such an assumption for microporous solids has been questioned in recent years, and in this study, we show that it is not applicable for the shale sample studied. We present a new method to measure the adsorption of shale-gas components in shales, which does not require the use of He to measure the solid’s skeletal volume. Since the proposed analysis method relies on the use of dynamic adsorption data, we also propose here a new zero-point correction method for the magnetic suspension balance, which is better suited for the analysis of such data. Here, we employ the new technique to the study of Argon adsorption in Marcellus Shales.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Spatial heterogeneity analyses of pore structure and mineral composition of Barnett Shale using X-ray scattering techniques

The spatial heterogeneity of pore structure and mineral composition at mu m to mm scales in mm to cm-sized shale samples complicates the laboratory measurements of porosity & pore size distribution and consequently reservoir quality evaluation. Traditional fluid invasion characterization methods typically take hours to days to get data and can only test relatively small samples (usually 2.54 cm diameter core plugs and mm-sized rock chips). Furthermore, the Xray scattering techniques at the Advanced Photon Source of the Argonne National Laboratory have the capability to non-destructively determine the pore structure and mineral composition of mm x mm area in a short time of seconds and to hold several to hundreds of mm 2 sized sample to conduct large area heterogeneity analysis in the short duration of hours. With the use of ultra-small angle X-ray scattering (USAXS), small-angle X-ray scattering (SAXS), and wide-angle X-ray scattering (WAXS), the porosity, surface area and pore size distribution of two Barnett Shale samples have been mapped out and the mineral compositions are determined qualitatively. Overall, the porosity and pore surface area of the Barnett Shale Sample A over a 36 cm2 area ranges from 1.70 % to 8.13 % and 8.87 m 2 /g to 40.2 m 2 /g respectively. The porosity and surface area of Sample B over a 24 cm 2 area varies from 3.15 % to 11.7 % and 18.3 m 2 /g to 60.2 m 2 /g. In Sample A, the mineral composition shows a shift from carbonate-rich to siliciclastic-rich over a distance of several millimeters. For Sample B, the mineral compositions are mainly siliciclastic and do not show an obvious lithological change. The direct observations of high spatial heterogeneity of pore structure and mineral composition in shale illustrate the utility of integrated X-ray scattering techniques to provide valuable insights into shale studies and reservoir evaluation.

58 GEOSCIENCES↗

Wetting mechanism and alteration of nano-sized shale pores: Insights from contrast variation small angle neutron scattering

Wettability of tight shale is crucial for fluid flow and mass transport process in energy geosciences. However, understanding the interfacial chemistry and wetting mechanisms at sub-nano-pore scales remains a formidable challenge. Here, in this study, the Contrast Variation technique of Small Angle Neutron Scattering (CV-SANS) is employed to investigate shale’s interfacial chemistry using reagents that possess a range of different polarities, including water, n-decane, toluene, and dimethyl methanamide. Through five different experimental strategies, we have demonstrated a successful modification of shale wettability, ranging from enhancement, weakening, to reversal. Delving into the mechanisms, we illustrated the crucial role of pre-existing liquid films in these changes, where the uniquely co-existing polar and non-polar functional groups in dimethyl methanamide acted as a conduit for interfacial chemistry adjustments. Furthermore, a solvent immersion led to matrix dilation as well as liberation of residual oil-occupied pores, resulting in altered pore size distributions, with hydrogen bonding playing a significant role in the polar groups. Interestingly, despite shale exhibiting a stronger affinity for oil over water, hydrophilic solvents induced more substantial dilation than lipophilic ones. Collectively, this work elucidates the dynamic change of interfacial chemistry via the configuration of polarity using chemical reagents, and the CV-SANS technique underscores its invaluable utilities in decoding the interfacial wettability traits in nanopore space of shale.

58 GEOSCIENCES↗

Initial Laboratory Measurements Probing Hydrogen Interactions with Eagle Ford Shale and Pyrite: Potential Implications for Subsurface Hydrogen Storage

Hydrogen (H 2 ) has the potential to be a transformative technology as an enabler to a low-carbon future and promoter of renewable energy. When H 2 is injected and stored in the subsurface, it has the potential to interact with the caprock (usually shale) which overlies and seals the storage reservoir. Here, this study examines geochemical reactions or changes in surface morphology to Eagle Ford Shale, a proxy for caprock, upon exposure to H 2 at 50°C and 10.3 MPa. Reactions were also performed with N 2 to provide an experimental control. Scanning Electron Microscopy with Energy Dispersive Spectroscopy (SEM-EDS), Atomic Force Microscopy (AFM), and Optical Photothermal-Infrared (O-PTIR) Spectroscopy were applied to quantify changes on the microscale and nanoscale level. Fluid chemistry changes were monitored with Ion Chromatography (IC) and Inductively Coupled Plasma Mass Spectrometry (ICP-MS). Exposure of Eagle Ford Shale to H 2 gas alone did not result in any alterations to the shale chemically or any changes in the surface morphology. Exposure of Eagle Ford Shale to both H 2 and water as well as N 2 and water resulted in changes to the surface morphology because of gypsum dissolution and reprecipitation, thus indicating that H 2 is not necessary to promote changes. Pure pyrite was the most reactive with H 2 possibly resulting in a reduction to pyrrhotite. These initial studies suggest that the extent of reactions activated by hydrogen with caprock are minor under the temperature and pressure conditions that would represent underground hydrogen storage.

08 HYDROGEN↗