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117 records · Page 7

Targeted Dy intercalation under graphene/SiC for tuning its electronic band structure

Metal intercalation of graphene is a promising method to tune its electronic band structure and generate novel electronic and topological phases. The tuning depends critically on the ability to bond the intercalated atoms at predesigned, subsurface interlayer locations because the emerging band structure depends on metal location. In this work, we have studied Dy intercalation under single-layer graphene (SLG) on SiC using spot profile analysis–low-energy electron diffraction and scanning tunneling microscopy (STM). The experimental work is complemented with density-functional theory (DFT) analysis. Because different diffraction spots originate from different subsurface interlayer regions, it is possible to identify changes in the intercalation location by monitoring the spot intensity as a function of growth conditions. DFT calculations of the chemical potential as a function of intercalated Dy coverage support the variation of the stability of the intercalated phase at different intercalated locations. The preferred location is confirmed from STM studies showing the removal of the 6 × 6 moiré corrugation at the preferred location, observed at higher Dy coverage.

2-dimensional systems↗

Coupled geomechanical investigation of depletion-induced fault reactivation

Fault reactivation during subsurface fluid production pose significant challenges to safe and sustainable resource extraction. Here, this study presents a three-dimensional coupled geomechanical framework to investigate the processes driving fault reactivation, capturing the interactions between reservoir dynamics and geomechanical responses. Verification against theoretical estimations based on linear poroelasticity confirms the model's capacity in representing reservoir background stress responses. However, the study reveals that relying solely on background stress states can underestimate or overestimate fault reactivation potential, emphasizing the importance of including localized stress perturbations such as differential compaction and stress redistribution. Applied to a fault (M1) inspired by the geological characteristics of the Groningen field, the model shows slip initiation at 2965 m depth with 16.0 MPa depletion, aligning with field observations where seismicity occurred at approximately 3 km depth after 15.8 MPa depletion. Parametric studies reveal: (1) inelastic reservoir compaction delays fault reactivation and mitigates fault slip by reducing stress concentration, (2) higher intermediate in-situ stress magnitudes decrease the Coulomb Failure Stress (CFS) increase rate and reduce fault slip, (3) larger fault offsets amplify shear stress near the offset zone, promoting earlier reactivation and longer rupture propagation, and (4) fault permeability significantly influences pressure diffusion, with low-permeability faults leading to sharper stress changes and earlier fault destabilization. These insights highlight the critical role of geological and mechanical parameters in fault reactivation and provide a predictive framework for mitigating induced seismicity risks.

Coupled geomechanical modeling↗

Factors controlling injection-induced rupture of intersecting faults during geological sequestration of CO 2

This study addresses coupled multiphase fluid flow and geomechanics effects on potential fault activation associated with subsurface CO 2 injection around intersecting faults. An enhanced fault-representation model is used to capture geomechanical responses of two intersecting faults with finite length during CO 2 injection. The faults are embedded in a strike-slip stress regime of a caprock-reservoir-basement system with the faults represented by zero-thickness interfaces with adjacent finite-thickness damage zones. A sensitivity analysis is conducted to study the effect of fault permeability, slip-weakening behavior, well location relative to the orientation of faults, and well placement (the number and location of injection wells). Five metrics (pressure, CO 2 plume, shear state on the fault, as well as shear displacement and stress path at selected fault monitoring points) are selected to assess CO 2 migration and reactivation of intersecting faults. The results show that induced ruptures are favored by low permeability faults due to high pressure buildup and by slip-weakening behavior resulting from fault strength reduction. The location of one injection well relative to fault orientation determines the magnitude of changes in effective normal stress and shear stress, affecting the location of induced ruptures. Well placement (two injection wells used in the paper) dominates pressure diffusion around the intersection and tips of faults. This redistributes changes in effective normal stress caused by each injection well, influencing the spatial distribution of ruptures along faults. A larger injection volume induces far-field ruptures that are controlled by stress transfer within the injection layer. The findings presented here can provide valuable insights into engineering operations for a long-term, safe, and reliable geologic CO 2 storage.

Fault permeability↗

The Influence of Aqueous Dispersivity on Transport of Radiological Material at LANL MDA G - 20450

Aqueous dispersivity is a phenomenon by which a solute moving in groundwater mixes with water that does not contain the solute and becomes diluted. Solutes take paths of varying lengths through pore networks or experience slower velocities due to interactions with pore walls. Aqueous dispersivity leads to breakthrough curves with earlier arrival than expected in purely advective systems and persistent 'tails,' or late-arriving, dilute concentrations of the solute. Dispersivity can be longitudinal (in the direction of flow) or transverse (orthogonal to flow). LANL has disposed of radioactive material at Material Disposal Area (MDA) G since the late 1950's. Most of the disposed materials at MDA G are low-level waste (LLW), but other types of radioactive wastes are disposed or stored at the site. For example, there is a collection of remote-handled transuranic waste (RH-TRU) waste in 33 shafts, which were intended to be stored retrievably. Aqueous-phase radionuclides included in models of contaminant transport at MDA G are subject to dispersive processes in porous media of the vadose zone and saturated zone. To model dispersivity at MDA G probabilistically, we created site-specific distributions of aqueous dispersivity. First, we performed a comprehensive review of peer-reviewed publications, reports from other performance assessments of MDA G, and documentation from sites that were considered similar based on expert opinion, such as Yucca Mountain. Data were included from a wide range of sources, so that distributions developed based on the data reflect the current state of knowledge in properties of the subsurface environment. Data were grouped based on value type (e.g., determined via experiment or used in a different model), rock type, zone type (saturated or unsaturated), and site, and were weighted in the distributions according to their relevance to the site and zone type. We combined Monte Carlo simulation and bootstrapping techniques to produce approximate distributions of mean aqueous dispersivity. Distributions of dispersivity for saturated and unsaturated zone transport are differentiated by data weight and the length scales over which transport occurs. We find that underestimating or disregarding transverse dispersivity may lead to overstating simulated well capture in the saturated zone at MDA G. Neglecting transverse dispersivity is a common assumption due in part to use of one-dimensional transport models that do not consider solute spreading orthogonal to flow. Also, we find that variability in longitudinal dispersivity is associated with substantial travel time alterations in the MDA G unsaturated zone and in simulated contaminant breakthrough times at a downstream observation plane in the MDA G saturated zone. Finally, at large scales (>1000 m), a linear trend between the dispersivity coefficient and length over which transport occurs may overestimate the dispersivity coefficient. Future modeling work with application to solute spreading could include interacting advective and diffusive zones in the highly fractured basalt below MDA G. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Confinement-Driven Heterogeneous Benzene Crystallization in Silica Nanopores

Nanoconfinement alters the thermodynamics, dynamics, and kinetics of fluids hosted in nanoscale solid nanopores to an extent that depends on the characteristics of the confining space and the chemistry of the confined fluids. Confinement-induced alterations in the phase behavior of confined energetic fluids under high pressure or low temperature are highly relevant to subsurface and subsea phenomena such as fluid flow in porous media, hydrate formation and dissociation, and gas storage capacity. Although extensive efforts have been directed toward understanding the phase behavior of confined fluids, the role of solid-liquid interfaces in the phase transitions of organic liquids has not been resolved yet. Here, we explore the onset and growth of benzene crystallization confined in 6 nm sized SBA-15 silica nanopores in the temperature range 300-200 K using in situ extended range small-angle and wide-angle X-ray scattering (SAXS/WAXS) measurements and atomistic classical molecular dynamics (MD) simulations. The crystallization onset of confined benzene depresses to 265 K compared to the freezing point of bulk benzene ( ~278 K), followed by the continuous growth of the emerged crystals in the pore space with complete crystallization at 200 K. The orientation of the emerged benzene crystals is dominated by parallel (π-π stacking) and perpendicular (T-shape stacking) orientations along the cylindrical pore radius and pore length, respectively. The onset of benzene crystals occurs heterogeneously on the pore surface and grows continuously toward the pore center. Further, confined benzene undergoes a dynamical crossover from fragile to strong dynamics behavior, inferred from the rotational and translational diffusion. The insights provided by this study have significant implications for the phase transitions of confined organic liquids that are relevant to a wide range of applications in the biological, geological, environmental, and chemical fields.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Rapid Simulation of Unconventional Reservoirs by Multidomain Multiresolution Modeling Based on the Diffusive Time of Flight

Summary The fast marching method (FMM)-based rapid flow simulation has been shown to accelerate simulation efficiency by orders of magnitude by transforming 3D simulation to equivalent 1D simulation using the concept of the “diffusive time of flight” (DTOF). However, the 1D transformation does not directly apply to multiwell problems. In this paper, we propose a novel DTOF-based multidomain multiresolution discretization scheme to accelerate multiwell simulation of unconventional reservoirs. Our method formulates multiwell simulation problems based on the DTOF which displays the pressure front propagation in unconventional reservoirs. The DTOF contours are used to partition the reservoir into local and shared domains. A local domain is where the flow is dominated by a single well, and the shared domain is where the fluid flow is influenced by multiple wells. The DTOF contours expand independently in local domains and interfere in the shared domain. After the partitioning, each domain is discretized using a multiresolution scheme whereby the original 3D fine mesh is preserved near the wells to account for detailed physics including gravity, and the rest of the domain is discretized into 1D mesh based on the DTOF contours to alleviate the simulation workload. The power and efficacy of our approach are demonstrated using synthetic and field-scale simulation models with different degrees of geologic and well-completion complexity. The simulation results, number of active cells, and computation time for the proposed discretization scheme are compared with the original high-fidelity 3D model for each case. The results show that the proposed method is suitable for multiwell simulation problems in unconventional reservoirs and can accelerate flow simulations by orders of magnitude with minimal loss of accuracy. The novelty of this work is the creation of DTOF-derived multiresolution discretization with local and shared domains to simplify and accelerate the calculation of subsurface flow problems, especially in unconventional reservoirs. Our workflow can be easily interfaced with commercial simulators, making it suitable for large-scale field applications.

Engineering↗

Reducing Cost of Chlorinated Volatile Organic Compound Remediation by Transitioning from Active to Passive Soil Vapor Extraction - 20157

Areas of high chlorinated volatile organic compound (cVOC) contamination at the Savannah River Site (SRS) have been undergoing remediation via soil vapor extraction, sometimes coupled with thermal treatments to enhance extraction rates. These active systems are effective in removing large amounts of contaminant mass from the subsurface and mitigating the impacts to groundwater. However, as extraction rates decline, costs must be evaluated with respect to the benefit of continued active operation. A decision framework for identifying conditions when a transition to a more passive remediation is appropriate has been developed with state and federal regulatory agencies. Two remediation areas have recently been transitioned from active soil vapor extraction (ASVE) to passive soil vapor extraction (PSVE) at the SRS. Performance evaluation goals including plume stabilization, overall mass removal trends, environmental sustainability and costs were considered in transitioning from active remediation to passive technologies at both sites. At the Dynamic Underground Stripping (DUS) project at the M-Area Settling Basin, ASVE was combined with steam injection to extract cVOCs during active operations. Steam injection occurred from September 2005 to September 2009. DUS utilized 63 steam injection wells, 34 active vapor extraction wells, and 3 active soil vapor extraction units (SVEUs). Two active SVEUs had 60 horsepower blowers; the third had a 25-horsepower blower. Mass removal was closely tracked during DUS operations; over 181,437 kilograms (400,000 pounds) of cVOCs were removed while active steam injection occurred. After steaming was stopped, ASVE continued. The 34 active wells were evaluated in 2012. The ASVE wells were grouped into categories of high, medium, and low extraction rates. High producing wells remained connected to a single active SVEU. Low producing wells were abandoned, and the medium producing wells were transitioned to PSVE (Microblowers{sup TM}). Microblowers{sup TM} utilize a dedicated blower per well and are solar powered. This passive technology provides energy, maintenance, and operation costs savings while still providing an efficient reduction in cVOC migration to groundwater. In 2018, the remaining ASVE wells were evaluated again. The purpose of this testing was to identify which wells removed the most mass. An optimal well configuration was determined. The criteria to discontinue ASVE was removal of less than 18 kilograms (40 pounds) per week of cVOCs. After 3 months of shutdown (rebound conditions), 2.7 kilograms (5.9 pounds) of cVOCs per week were being removed. Data from the rebound test justified ending ASVE and transitioning wells with higher extraction rates to PSVE. Wells that had depleted the cVOC mass within their zone of influence were abandoned. Performance data from existing PSVE wells justified ending PSVE at wells with depleted extraction rates. Currently the system has 16 PSVE wells operating. Another ASVE system was being used to treat cVOC contaminated soil at the A-Area Miscellaneous Rubble Pile (AMRP) at SRS. System operation began in 2004, with 7 ASVE wells connected to a 60- horsepower blower. Mass removal rates and contaminant concentrations remained consistently low over the ASVE lifespan at AMRP. This indicated that mass removal was diffusion limited. With this data, the 7 ASVE wells were transitioned to PSVE in 2017. Twelve pressure monitoring points were also transitioned to PSVE wells. AMRP currently has 19 PSVE wells operating. Both transitions from active to passive remediation had concurrence from the United States Environmental Protection Agency and the South Carolina Department of Health and Environmental Control. These transitions ensure that only the necessary amount of energy is being exerted to remediate the environment. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Explosive Byproduct Gas Transport Through Sorptive Geomedia

Current underground nuclear explosion (UNE) detection strategies rely heavily on atmospheric noble gas sampling of radioxenon. However, discriminating nuclear weapons testing programs from civilian sources is difficult due to highly variable atmospheric radioxenon backgrounds and processes affecting subsurface transport of parent radionuclides. Here, we aim to study the transport of gases produced by subsurface explosions as novel stable signatures for underground nuclear explosion (UNE) monitoring. These gases may be produced in large quantities with distinct molecular ratios, which will be impacted by subsurface transport processes. To demonstrate how ratios of gases produced by explosions can change during transport in geomaterials, we conducted laboratory benchtop experiments on the transport of carbon dioxide (CO 2 ) and hydrogen (H 2 ) gases through variably saturated zeolitic tuff, which is abundant at the historic US testing site. We observed that zeolitic tuff sorbs substantial quantities of CO 2 while allowing H 2 to transport more freely, leading to changes in the molecular ratios of the two gases along the transport pathway. Gas uptake in the dry zeolitic tuff core was 72.3% for CO 2 , compared with 53.4% for xenon and 7.6% for H 2 . The presence of 20% water saturation disrupted the CO 2 sorption process, though to a lesser extent than observed for noble gases, with a 36.7% drop in xenon sorption compared with a 21.9% drop for CO 2 . These results represent the first observations of zeolite sorption altering explosive gas ratios during transport through geomedia relevant to nuclear proliferation monitoring.

54 ENVIRONMENTAL SCIENCES↗

Evaluation of Zero-Net-Rate Pumping Tests

Accurately estimating the distribution of aquifer properties is key to understanding contaminant movement in the subsurface. The distribution of aquifer properties is typically addressed using slug or constant-rate well tests, and the pros and cons of these tests are well known. Slug tests are appealing because they avoid removing contaminated water, but their results are affected by well skin and the small volume of displaced water limits the volume of aquifer that can be evaluated. Constant-rate well tests have the disadvantage of requiring disposal of potentially contaminated water, but they can generate properties that are more representative than slug tests, and they can be used to estimate well efficiency and storativity, which are difficult to characterize using slug tests. Periodic pumping tests are appealing because they have many of the advantages and few of the disadvantages of slug and constant-rate well tests. Periodic pumping tests involve cycling the pumping rate with a regular period and measuring the resulting response in monitoring wells. Some of these tests involve imposing a periodic rate on a constant mean rate. However, other tests involve moving water out and back into the well at rates that are balanced so the net rate after each period is zero. Some zero-net-rate (ZNR) well tests use rates that follow a sinusoidal pattern, whereas others use a square wave pattern that switches between a constant rate of pumping and a constant rate of injection to achieve a zero-net rate. ZNR well tests appear to be a useful compromise between slug and constant rate tests, but methods for conducting and analyzing the results from these tests have received limited evaluation. Periodic pumping tests are typically evaluated through recorded pressure responses to a disturbance source. Recent work has demonstrated that the strain field in the vadose zone shows a response to disturbances in the underlying aquifer. Various instrument designs are available that can record vertical and horizontal strain to very precise resolutions (10-9 ε). Measuring the strain in the vadose zone can present lower costs than measuring pressure in a monitoring well, so using strain could improve the resolution of ZNR tests, as well as make these tests potentially cheaper. A ZNR periodic pumping system was constructed and used to perform tests in the Clemson, South Carolina area. The system was designed to pump and inject with a periodic square-wave, so pumping occurs at a constant rate for half the period and is followed by injection at the same rate for half the period resulting in no net gain or loss of water from the aquifer. The system is designed to generate flow rates from 1 to 3.5 gallons per minute (gpm) with a capacity of 875-gallon per half period. Pressure and strain monitoring points are located in the vicinity of the pumping well. A series of 10 ZNR periodic pumping tests were conducted at the field site, with periods ranging from 2 to 540 minutes. Pressure data were collected and recorded in four monitoring wells in various locations around the pumping well. In addition, vertical and horizontal strain and tilt data were recorded in various locations around the pumping well. Traditional aquifer tests, including slug tests and constant-rate pumping tests were conducted at the field site to provide a baseline of aquifer parameter estimates that are compared the results of ZNR tests. Pressure data measured at monitoring wells during ZNR tests were analyzed utilizing an analytical solution (Streltsova, 1988) that assumes a confined aquifer and estimates hydraulic diffusivity and transmissivity using the time lag and amplitude of the pressure signal. The storativity can be separated out from the hydraulic diffusivity using the transmissivity estimate. The time-lag and amplitude of the pressure signals were estimated using a Fourier transform. The time-lag of the primary period of the pressure increases as a linear function of distance from the pumping well, and it increases as the square root of the period of the ZNR test over a range of periods spanning two orders of magnitudes. The first few harmonics follow similar trends, but the higher frequency harmonics diverge from this trend. Strain and tilt data from various instruments in the vadose and saturated zones are periodic during ZNR tests. The time lags of the strain components increase roughly linearly with distance from the well. Many of the time lags of the strain data from the vadose zone are similar to the time lags observed in the pressure data from a similar distance and pumping period. Theoretical experiments were performed to understand how pressure and strain responds to ZNR periodic pumping. The time-lags of the simulated pressure responses match the field data trends. The results were used to validate the Streltsova (1988) solution for periodic pumping to estimate hydraulic diffusivity. Hydraulic diffusivity was estimated to be 1.8 x 10-2 m2s-1 < Dh < 9.0 x 10-2 m2s-1 using pressure data from all the wells during ZNR tests. Transmissivity was estimated to be 0.8 x 10-4 m2s-1 < T < 4.3 x 10-4 m2s-1. Assuming Storativity = T/Dh gives 1.1 x 10-3 < S < 19 x10-3. Transmissivity is used to estimate the hydraulic conductivity, K, by dividing by the assumed aquifer thickness. Two constant-rate pumping tests were conducted and analyzed using two conceptual models: The Hantush (1961) solution was used to analyze data assuming confined conditions and the Neuman (1974) solution was used to analyze data assuming unconfined conditions. The Hantush (1961) solution estimated transmissivity to be 1.6 x 10-4 m2s-1 < T < 1.8 x 10-4 m2s-1 when using data from all the wells. Storativity was estimated to be 4.4 x 10-3 < S < 8.2 x 10-3. Assuming Dh = T/S gives 0.22 x 10-2 m2s-1 < Dh < 3.6 x 10-2 m2s-1. The Neuman (1974) solution estimated transmissivity to be 0.80 x 10-4 m2s-1 < T < 0.84 x 10-4 m2s-1. Total storativity (S + Sy) was estimated to be 22 x 10-3 < S < 110 x 10-3. Storativity excluding the Sy term was estimated to be 2.2 x 10-3 < S < 2.5 x 10-3. Assuming Dh = T/S gives 0.073 x 10-2 m2s-1 < S < 0.36 x 10-2 m2s-1. Two slug tests were performed on the pumping well, PW-2. The Bouwer and Rice (1976) solution for slug tests was used to analyze the data. This solution works for both confined and unconfined conditions, so both conceptual models were covered through the analysis. Hydraulic conductivity was estimated to be 1.95 x 10-6 ms-1 < K < 2.49 x 10-6 ms-1. Statistical comparison show generally no significant difference in the estimates of Dh, K, or S made using ZNR and conventional pumping tests.. However, the total storage estimated by the Neuman (1974) solution for unconfined settings is larger than that estimate using the Streltsove analysis applied to the ZNR tests. This is likely because the Neuman solution considers delayed yield from storage that the water table, whereas the Streltsova (1988) solution assumes confined conditions. The analysis also indicates that there is a statistically significant difference between parameters estimated with conventional slug tests and those measured with either constant-rate pumping tests or ZNR tests. Hydraulic diffusivity is estimated from the time-lag and the distance from the well. The time-lags of the strain data from the vadose zone are similar to the lags of the pressure data from a similar distance. This indicates that hydraulic diffusivities estimated from the strain data measured in the vadose zone would be similar to the estimates from the pressure data measured in the aquifer. There appear to be sign reversals in some of the strain data that were corrected to estimate the time lag. The dissolved oxygen (CO) concentration was measured during several ZNR tests to evaluate the feasibility of using the procedure to increase contaminant degradation kinetics that are related to DO. The results indicate that DO can be increased during the cycling of ZNR tests in some cases.

Smith-Jones, Austin↗