Core Hole Research Articles

Investigations on Unconventional Tight Carbonate Rock Cores by Low-Field Nuclear Magnetic Resonance Relaxometry

Investigations on Unconventional Tight Carbonate Rock Cores by Low-Field Nuclear Magnetic Resonance Relaxometry

Observation of molecular resonant double-core excitation driven by intense X-ray pulses

The ultrashort and intense pulses of X-rays produced at X-ray free electron lasers (XFELs) have enabled unique experiments on the atomic level structure and dynamics of matter, with time-resolved studies permitted in the femto- and attosecond regimes. To fully exploit them, it is paramount to obtain a comprehensive understanding of the complex nonlinear interactions that can occur at such extreme X-ray intensities. Herein, we report on the experimental observation of a resonant double-core excitation scheme in N2, where two 1σ core-level electrons are resonantly promoted to unoccupied 1πg*\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$1{\\pi }_{g}^{* }$$\\end{document} molecular orbitals by a single few-femtosecond broad-bandwidth XFEL pulse. The production of these neutral two-site double core hole states is evidenced through their characteristic decay channels, which are observed in good agreement with high-level theoretical calculations. Such multi-core excitation schemes, benefiting from the high interaction cross sections and state- and site-selective nature of resonant X-ray interactions, should be generally accessible in XFEL irradiated molecules, and provide interesting opportunities for chemical analysis and for monitoring ultrafast dynamic processes.

Subsurface Microbial Colonization at Mineral-Filled Veins in 2-Billion-Year-Old Mafic Rock from the Bushveld Igneous Complex, South Africa

Recent advances in subsurface microbiology have demonstrated the habitability of multi-million-year-old igneous rocks, despite the scarce energy supply from rock-water interactions. Given the minimal evolution coupled with exceedingly slow metabolic rates in subsurface ecosystems, spatiotemporally stable igneous rocks can sustain microbes over geological time scales. This study investigated a 2-billion-year-old mafic rock in the Bushveld Igneous Complex, South Africa, where ultradeep drilling is being executed by the International Continental Scientific Drilling Program (ICDP). New procedures were successfully developed to simultaneously detect indigenous and contaminant microbial cells in a drill core sample. Precision rock sectioning coupled with infrared, fluorescence, and electron microscopy imaging of the rock section with submicron resolution revealed microbial colonization in veins filled with clay minerals. The entry and exit of microbial cells in the veins are severely limited by tight packing with clay minerals, the formation of which supplies energy sources for long-term habitability. Further microbiological characterization of drilled rock cores from the Bushveld Igneous Complex will expand the understanding of microbial evolution in deep igneous rocks over 2 billion years.

Enhance Oil Recovery by Carbonized Water Flooding in Tight Oil Reservoirs

The low permeability of tight sandstone reservoirs limits the application of water flooding to enhance oil recovery. Due to the properties of CO2, people improve crude oil recovery by carbonizing water flooding. However, many studies have not prioritized determining the concentration of carbonated water before comparing the recovery rates of carbonated water flooding and pure water flooding after water flooding. This article takes the Chang 6 oil reservoir as the research object, and uses a combination of nuclear magnetic resonance testing and displacement experiments to conduct experiments on optimizing the concentration of carbonated water. Based on this, experiments on water flooding and carbon water flooding after water flooding to improve crude oil recovery are conducted to compare and analyze the oil enhancement potential of carbonated water flooding. The experimental results show that the physical properties, pore throat structure and seepage capacity of sandstone samples of type I, II and III decrease in turn. With the increase of carbonated water concentration, the expansion coefficient, viscosity reduction rate, contact angle reduction rate and core permeability loss rate of crude oil increase. The damage rate of 0.4mmol/cm3 carbonated water solution (17.6g CO2: 1L water) to the core permeability is only 0.98%, which is the optimal experimental concentration. During the water flooding process, crude oil in pores of different scales in Type I rock cores is utilized, and the degree of utilization in large pores is relatively high. Continuing to use carbonated water to drive oil in the rock cores after water flooding increased the recovery rate of crude oil by 15.24%; The degree of crude oil utilization in small pores of Tpye II core after carbonization and water flooding increased by 29.4%, and the final recovery rate of crude oil increased by 11.35% compared to the core after water flooding; The physical properties of Tpye III core are poor, with a small proportion of large pores, resulting in a 9.04% increase in crude oil recovery rate. Compared with pure water flooding, the recovery rate and utilization degree of large and small pores in the three types of rock cores after carbonization water flooding have been improved to varying degrees. Among them, the utilization degree of crude oil in large pores is the most significant, which increases the recovery rate of crude oil in the rock core after displacement. This study can provide a theoretical basis for improving crude oil recovery by carbonizing water flooding.

Elucidating Anomalous Intensity Ratios in Chlorine L-Edge X-ray Absorption Spectroscopy: Multiplet Effects and Core Rydberg Transitions.

A relativistic core-valence-separated equation-of-motion coupled cluster (CVS-EOM-CC) study of chlorine L2,3-edge X-ray absorption near-edge structure (XANES) spectra using CH3Cl and CH2ICl as representative molecules is reported. The nearly identical intensity for the main features in the L2- and L3-edge XANES spectra is attributed to multiplet effects and the overlap between core-valence and core Rydberg transitions. The multiplet effects originating from the interaction between the core hole and the C-Cl σ* orbitals account for around half of the deviation of the L3 and L2 intensity ratio from the 2:1 ratio of the numbers of 2p3/2 and 2p1/2 electrons. The 2p3/2 → 4s core Rydberg transitions are shown to overlap with the 2p1/2 → σ* transitions and contribute to the other half of the intensity anomaly. We demonstrate that triple excitations in CVS-EOM-CC calculations play important roles in accurate simulation of the overlap between the 2p1/2 → σ* and 2p3/2 → 4s transitions.

Core‐flooding experiments of various concentrations of CO2/N2 mixture in different rocks: II. Effect of rock properties on residual water

AbstractDuring CO2 storage in deep saline aquifers, the presence of residual water has an important influence on the storage efficiency and safety. In this study, natural rock cores taken from deep reservoirs in the Ordos Basin and Fukang, Xinjiang are used as research objects. Nine groups of core‐flooding experiments are performed under different CO2/N2 gas mixture ratios to study the influence of rock properties (mineral composition, permeability, porosity and pore structure) on the residual water. Furthermore, the geophysical and chemical properties of rock cores are analyzed by X‐ray diffraction, electron microscopy, field emission scanning electron microscopy and piezoelectric mercury method. The results show that residual water saturation is a quantitative power function of drainage time. The residual water saturation is positively correlated with the total amount of quartz and feldspar and increases with increasing permeability. Moreover, both the average and median pore throat radius show a strong inverse correlation with irreducible residual water saturation; as these radius increase, the residual water saturation decreases. In contrast, the porosity and maximum pore throat radius display a weaker correlation with irreducible residual water saturation. This study is of great value for engineering practices such as the site selection of CO2 storage projects in saline aquifer and improvement of CO2 storage efficiency. © 2024 Society of Chemical Industry and John Wiley & Sons, Ltd.

Research on microscale displacement characteristics of supercritical CO2 fracturing in shale oil reservoirs

AbstractThe great success of CO2 fracturing in shale oil reservoirs has not only increased the production capacity of shale oil, but also effectively carried out CO2 geological storage. In this paper, focusing on the microscale displacement characteristics of CO2 fracturing in shale oil reservoirs, first, the impact of oil saturation and gas invasion pressure on gas invasion is discussed. Then, the coupling control mode of oil saturation/pressure for various mechanisms of gas invasion is revealed. Results show that: (a) at lower displacement, the rock core has a lower initiation pressure and is fractured in a shorter period of time; (b) at higher displacement, the required fracturing time is longer and the fracturing pressure increases, but the fracturing effect is good and it is easy to form complex fracture networks; and (c) under higher pressure conditions, more complex fractures can be formed, which is beneficial for reservoir transformation and production improvement.

X-ray circular dichroism measured by cross-polarization x-ray transient grating

Abstract Measuring natural circular dichroism in the x-ray regime to extract stereochemical information from chiral molecules in solution remains a challenge. This is primarily due to technical limitations of the existing synchrotron sources, which hinder access to measurements of local chirality by exploiting core hole electronic transitions. In response to this challenge, we propose an alternative approach: utilizing XFEL-based cross-polarization x-ray transient grating (XTG). This method provides an indirect means to measure x-ray circular dichroism (XCD). Notably, our findings reveal that the signal emerges only once the excited cores have undergone dephasing through relaxation. XTG is now routinely measured in the XUV regime and has recently been made available for hard x-rays. Free electron lasers now offer polarization controls, and XTG can be extended to various polarization states for the two pump beams, making XCD measured by XTG feasible with the current state-of-the-art technology.

Micro–Nano 3D CT Scanning to Assess the Impact of Microparameters of Volcanic Reservoirs on Gas Migration

Volcanic rock reservoirs for oil and gas are known worldwide for their considerable heterogeneity. Micropores and fractures play vital roles in the storage and transportation of natural gas. Samples from volcanic reservoirs in Songliao Basin, CS1 and W21, belonging to the Changling fault depression and the Wangfu fault depression, respectively, have similar lithology. This study employs micro–nano CT scanning technology to systematically identify the key parameters and transport capacities of natural gas within volcanic reservoirs. Using Avizo 2020.1software, a 3D digital representation of rock core was reconstructed to model pore distribution, connectivity, pore–throat networks, and fractures. These models are then analyzed to evaluate pore/throat structures and fractures alongside microscopic parameters. The relationship between micropore–throat structure parameters and permeability was investigated by microscale gas flow simulations and Pearson correlation analyses. The results showed that the CS1 sample significantly exceeded the W21 sample in terms of pore connectivity and permeability, with connected pore volume, throat count, and specific surface area being more than double that of the W21 sample. Pore–throat parameters are decisive for natural gas storage and transport. Additionally, based on seepage simulation and the pore–throat model, the specific influence of pore–throat structure parameters on permeability in volcanic reservoirs was quantified. In areas with well–developed fractures, gas seepage pathways mainly follow fractures, significantly improving gas flow efficiency. In areas with fewer fractures, throat radius has the most significant impact on permeability, followed by pore radius and throat length.

Advanced classification of drill core rock type and weathering grade using detection transformer-based artificial intelligence techniques

Rock classification plays a crucial role in various fields such as geology, engineering, and environmental studies. Employing deep learning AI (artificial intelligence) methods has a high potential to significantly improve the accuracy and efficiency of this task. The paper delves into the exploration of two cutting-edge AI techniques, namely Mask DINO and Mask R-CNN (convolutional neural network), as means to identify rock weathering grades and rock types. The results demonstrate that Mask DINO, which is a Detection Transformer (DETR), outperforms Mask R-CNN for the aforementioned purposes. Mask DINO achieved f-1 scores of 91% and 86% in weathering grade detection and rock type detection, as opposed to the Mask R-CNN’s f-1 scores of 84% and 75%, respectively. These findings underscore the substantial potential of employing DETR algorithms like Mask DINO for automatic classification of both rock type and weathering states. Although the study examines only two AI models, the data processing and other techniques developed in this study may serve as a foundation for future advancements in the field. By incorporating these advanced AI techniques, logging personnel can obtain valuable references to aid their work, ultimately contributing to the advancement of geological and related fields.

Simulation Study on the Heat Transfer Characteristics of Oil Shale under Different In Situ Pyrolysis Methods Based on CT Digital Rock Cores

Simulation Study on the Heat Transfer Characteristics of Oil Shale under Different In Situ Pyrolysis Methods Based on CT Digital Rock Cores

Strontium isotopes in the atmosphere, geosphere and hydrosphere: Developing a systematic “fingerprinting” framework of rocks and water in sedimentary basins in eastern Australia

Understanding the connection between aquifers, aquitards, and groundwater-dependant ecosystems remains a key challenge when developing a conceptual hydrogeological model. The aim of this study was to develop a systematic strontium isotope (87Sr/86Sr) fingerprinting framework of rocks and water within the sedimentary Surat and Clarence-Moreton basins (SCM basins) in eastern Australia – an area of extensive coal seam gas development and high potential for aquifer and groundwater-surface water connectivity. To do this, new groundwater samples (n = 298) were collected, analyzed and integrated with published data (n = 154) from the basins' major sedimentary, volcanic and alluvial aquifers, including the major coal seam gas target, the Walloon Coal Measures. Samples were also analyzed from rainfall (n = 2) and surface water (n = 40). In addition, rock core samples (n = 39) from exploration and stratigraphic wells were analyzed to determine the range of Sr isotope composition from host rocks. The analyses of cores demonstrate a distinct and systematic contrast in 87Sr/86Sr between different hydrogeological units. This confirms that all major hydrogeological units have a narrow range with unique 87Sr/86Sr population characteristics that are useful for guiding conceptual model development. Comparison with selected hydrochemical and groundwater age tracers (14C and 36Cl) suggests only limited changes of 87Sr/86Sr from recharge beds to the deeper parts of the basins or with a decrease in natural 14C and 36Cl tracer content along flow paths. Stream sampling during baseflow conditions confirms that 87Sr/86Sr in surface waters are similar to those of the underlying bedrock formations. We demonstrated that 87Sr/86Sr analyses of rocks and water provide a powerful hydrostratigraphic and chemostratigraphic fingerprinting framework in the SCM basins, enabling reliable assessments of plausible aquifer and groundwater-surface water interconnectivity pathways. Applied in other complex multi-aquifer sedimentary basins in Australia, and globally, a similar approach can help to constrain conceptual hydrogeological models and facilitate improved water resource management.

Investigation on the plugging mechanism of nanocomposite polyacrylate copolymers in water-based drilling fluids: Experiments and applications

The plugging of nanopores and cracks in shale formation has become the critical technology that promotes the development of shale gas. Herein, nanocomposite polyacrylate (Poly-TALC) copolymers were successfully prepared by emulsion polymerization using butyl acrylate and triallyl isocyanurate as the raw material. Poly-TALC was characterized by fourier transform infrared spectroscopy (FTIR), laser light scattering particle size analysis, scanning electron microscope (SEM) and thermogravimetric analysis (TGA). The rheological properties and plugging performance of Poly-TALC were evaluated by a six-speed rotational viscometer, filter cake permeability test, core permeability test and pressure transfer experiment. Results revealed that Poly-TALC exhibited a particle size distribution ranging from 75.27 to 95.29 nm, while maintaining notable stability at 327.75 °C. Upon the addition of Poly-TALC to the drilling fluid, both the apparent viscosity and plastic viscosity insignificantly changes. At a Poly-TALC dosage of 1.0%, the filter cake's permeability was 1.2 × 10−5 μm2 with a plugging rate of 56.9%, while the permeability of the core was 1.2 × 10−6 μm2 with a plugging rate of 84.0%. The decrease in permeability was not significant beyond a Poly-TALC dosage of 1.0 wt%. Pressure transfer experiments demonstrate that Poly-TALC is able to form a multi-stage dense seal within the rock core, which can effectively prevent formation water from immersing into shale formation and improve shale wellbore stability.

Simulation of the effects of pile-rock breakwaters on the coastal sediment transport at Ganh-Hao beach, Bac-Lieu province, Vietnam

Abstract In recent years, the flat riverside coastal area of the Mekong Delta has been dealing with complex issues related to erosion and the buildup of sediment. Numerous research efforts have been undertaken to propose ways to address the adverse effects of shoreline erosion. One of these proposed solutions involves the construction of various types of breakwaters. A contemporary approach includes a design featuring concrete piles combined with a rock core, which has shown promising initial results in reducing wave impact and promoting sediment accumulation behind the structure. This study adopts a quantitative approach to examine how this structure influences sedimentation and erosion processes, the movement of suspended sandy sediments, and the seafloor within the zone extending from the structure to the shore. The research team utilized the Telemac numerical model, which combines dynamic hydrological calculations with simulations of coastal waves and sediment transport. The simulation results indicate a noticeable reduction in the concentration of suspended sandy sediments and an enhancement in sediment deposition in the area behind the coastal structure.

Strongly Negative Low‐Field Variation of Magnetic Susceptibility: Rock Magnetic Character of the Basement‐Cover Interface of Northeastern Oklahoma

AbstractSome rock and soil samples exhibit significant loss of magnetic susceptibility (χ) with increasing applied field amplitude even at relatively low (10–100s of A/m) fields, a behavior which remains unexplained. Exceptionally strong negative field‐dependence of susceptibility (χHD) is present in sandstones and altered intermediate‐felsic igneous rocks in several cores from the northeastern Oklahoma subsurface. These same rocks also show elevated frequency‐dependence of susceptibility (χFD), with reasonable correlation of χHD to χFD, and frequency‐dependent χHD. Results from multiple characterization methods indicate that strongly negative χHD in these rocks is linked to a yet‐unidentified phase which begins the approach to magnetic saturation in low fields (<1 mT/800 A/m), shows elevated χFD to low temperatures, is unstable at high temperatures, possesses significant anisotropy of magnetic susceptibility, and becomes paramagnetic above ∼83°C. Clear associations with fluid alteration features indicate that this material may be highly relevant to rock alteration, diagenetic, and environmental studies.

Numerical simulations of the acoustic and electrical properties of digital rocks based on tetrahedral unstructured mesh

Abstract Unconventional reservoirs typically exhibit strong heterogeneity leading to a significant scale effect in digital rock physics simulations. To ensure the reliability of the simulation results, improving computational efficiency and increasing sample sizes are crucial. In this study, we present a numerical finite element simulation method for the acoustic and electrical properties of digital rock cores based on tetrahedral unstructured meshes. We calculated the elastic moduli and electrical resistivity of the Fontainebleau sandstone digital rock samples. A comparison was made between the tetrahedral mesh and the traditional voxel-based hexahedral mesh in terms of the accuracy and efficiency of finite element numerical simulations. The results indicate that this numerical simulation method based on the tetrahedral mesh exhibits high accuracy comparable to experimental results, and its computational efficiency is significantly improved compared to the traditional hexahedral mesh method. These findings highlight the advantages of this finite element simulation method in improving the computational scale and efficiency of digital rock simulations. It effectively addresses common computational resource constraints in dealing with large-scale core systems and facilitates better integration with engineering construction, well-logging instrument simulations, and production applications.

Core Hole Effect to Valence Excitations: Tracking and Visualizing the Same Excitation in XPS Shake-Up Satellites and UV Absorption Spectra.

Introducing a core hole significantly alters the electronic structure of a molecule, and various X-ray spectroscopy techniques are available for probing the valence electronic structure in the presence of a core hole. In this study, we visually demonstrate the influence of a core hole on valence excitations by computing the ultraviolet absorption spectra and the shake-up satellites in X-ray photoelectron spectra for pyrrole, furan, and thiophene, as complemented by the natural transition orbital (NTO) analysis over transitions with and without a core hole. Employing equivalent core hole time-dependent density functional theory (ECH-TDDFT) and TDDFT methods, we achieved balanced accuracy in both spectra for reliable comparative analysis. We tracked the same involved valence transition in both spectra, offering a vivid illustration of the core hole effect via the change in corresponding particle NTOs introduced by a 1s core hole on a Cα, Cβ, or O atom. Our analysis deepens the understanding of the core hole effect on valence transitions, a phenomenon ubiquitously observed in general X-ray spectroscopic analyses.

Self-centering dual rocking core system with viscous dampers in additional rocking sections

To mitigate the high mode effects and reduce the force requirements of the structural members in the multi-story self-centering dual rocking core (SDRC) system, this paper proposes the multiple self-centering dual rocking core system with viscous dampers in additional rocking sections (MSDRCV system). The sketch and ideal working mechanisms of the MSDRCV system are interpreted. The additional rocking sections are set to decrease the force requirements of structural members and viscous dampers are included to mitigate high mode responses of the additional rocking sections, introducing seismic performance enhancement. Comparative analyses on a 9-story MSDRCV system with viscous dampers in rocking sections, a 9-story multiple self-centering dual rocking core system without viscous dampers in rocking sections (MSDRC system) and a 9-story SDRC system were carried out. The MSDRCV and MSDRC system can realize the reduction of the force demands in structural members in contrast to the SDRC system. Nevertheless, the high mode responses caused the uncontrollable displacement concentration in the MSDRC system and hence aggravated the seismic performance under rare seismic events. The analysis results in the frequency domain confirmed that the viscous dampers in the MSDRCV system can efficiently control the high-mode responses. The effects of the design parameters of the viscous dampers on the peak responses of the MSDRCV systems were comprehensively studied via parametric analyses. The results offer guidance for the viscous dampers design.

Geologic and Tectonic Controls on Deep Fracturing, Weathering, and Water Flow in the Central California Coast Range

AbstractThe creation of fractures in bedrock dictates water movement through the critical zone, controlling weathering, vadose zone water storage, and groundwater recharge. However, quantifying connections between fracturing, water flow, and chemical weathering remains challenging because of limited access to the deep critical zone. Here we overcome this challenge by coupling measurements from borehole drilling, groundwater monitoring, and seismic refraction surveys in the central California Coast Range. Our results show that the subsurface is highly fractured, which may be driven by the regional geologic and tectonic setting. The pervasively fractured rock facilitates infiltration of meteoric water down to a water table that aligns with oxidation in exhumed rock cores and is coincident with the adjacent intermittent first‐order stream channel. This work highlights the need to incorporate deep water flow and weathering due to pervasive fracturing into models of catchment water balances and critical zone weathering, especially in tectonically active landscapes.

Quantitative Characterization of Adhesion Work on Shale Surfaces and Discussion on the Influence of Roughness Based on Atomic Force Microscopy (AFM).

Adhesion is an intrinsic property of rocks and liquids. Investigating the factors contributing to its formation and the mechanisms governing its action is crucial for elucidating the adhesion work between solids and liquids. The adhesion work, serving as a parameter that characterizes the energy changes during the solid-liquid contact process, is a vital tool for probing this phenomenon. However, conventional measurements of the adhesion work are significantly influenced by surface roughness and fail to differentiate local variations in the adhesion performance. This limitation obscures our understanding of the primary adsorption sites and mechanisms between solids and liquids, posing significant challenges to the study of rock surface properties. In this study, in conjunction with scanning electron microscopy and contact angle analyses, we elucidated for the first time the locations where voids form during the solid-liquid contact process, the lithological composition of rough areas, and their impact on the adhesion work between water/oil and the surfaces. Additionally, employing atomic force microscopy (AFM), we examined the variations in water/oil-solid adhesion work across different characteristic regions, thereby characterizing the overall hydrophilic/hydrophobic properties of the rock core. Specific conclusions are as follows: (1) A negative correlation exists between roughness and the contact angle adhesion work, with heterogeneity impeding liquid-rock contact; (2) By comparing the strength of water-solid/oil-solid adhesion work within localized areas, we delineated the adhesion work characteristics of samples and their primary generation sites, with oil-solid adhesion work in target blocks predominantly originating from quartz, clay minerals, and organic matter; (3) The influence of pore throat development on the overall adhesion work of samples was clarified, demonstrating that an increase in the proportion of internal rock pores enhances the surface oil-solid adhesion work; (4) A dimensionless wetting index I was established to mitigate the impact of roughness on the expression of adhesion work, exhibiting a strong correlation with traditional evaluation methods.