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At least 577 records · Page 32

Gravity-driven controls on fluid and carbonate precipitation distributions in fractures

Abstract Many challenges related to carbon-dioxide ( $$\hbox {CO}_2$$ CO 2 ) sequestration in subsurface rock are linked to the injection of fluids through induced or existing fracture networks and how these fluids are altered through geochemical interactions. Here, we demonstrate that fluid mixing and carbonate mineral distributions in fractures are controlled by gravity-driven chemical dynamics. Using optical imaging and numerical simulations, we show that a density contrast between two miscible fluids causes the formation of a low-density fluid runlet that increases in areal extent as the fracture inclination decreases from 90 $$^\circ$$ ∘ (vertical fracture plane) to 30 $$^\circ$$ ∘ . The runlet is sustained over time and the stability of the runlet is controlled by the gravity-driven formation of 3D vortices that arise in a laminar flow regime. When homogeneous precipitation was induced, calcium carbonate covered the entire surface for horizontal fractures (0 $$^\circ$$ ∘ ). However, for fracture inclinations greater than 10 $$^\circ$$ ∘ , the runlet formation limited the areal extent of the precipitation to less than 15% of the fracture surface. These insights suggest that the ability to sequester $$\hbox {CO}_2$$ CO 2 through mineralization along fractures will depend on the fracture orientation relative to gravity, with horizontal fractures more likely to seal uniformly.

54 ENVIRONMENTAL SCIENCES↗

In-situ experiment reveals CO2 enriched fluid migration in faulted caprock

Abstract The sealing characteristics of the geological formation located above a CO 2 storage reservoir, the so-called caprock, are essential to ensure efficient geological carbon storage. If CO 2 were to leak through the caprock, temporal changes in fluid geochemistry can reveal fundamental information on migration mechanisms and induced fluid–rock interactions. Here, we present the results from a unique in-situ injection experiment, where CO 2 -enriched fluid was continuously injected in a faulted caprock analogue. Our results show that the CO 2 migration follows complex pathways within the fault structure. The joint analysis of noble gases, ion concentrations and carbon isotopes allow us to quantify mixing between injected CO 2 -enriched fluid and resident formation water and to describe the temporal evolution of water–rock interaction processes. The results presented here are a crucial complement to the geophysical monitoring at the fracture scale highlighting a unique migration of CO 2 in fault zones.

Science & Technology - Other Topics↗

Assessing the potential of composite confining systems for secure and long-term CO 2 retention in geosequestration

A potential geologic target for CO 2 storage should ensure secure containment of injected CO 2 . Traditionally, this objective has been achieved by targeting reservoirs with overlying seals-regionally extensive, low permeability units that have been proven capable of retaining buoyant fluid accumulations over geologic time. However, considering that the amount of CO 2 is limited by a decadal injection period, vertical migration of CO 2 can be effectively halted by a composite system of discontinuous shale/silt/mudstone barriers in bedded sedimentary rocks. Here, we studied the impact of depositional architectures in a composite confining system on CO 2 migration and confinement at reservoir scale. We stochastically generated lithologically heterogeneous reservoir models containing discontinuous barriers consistent with statistical distributions of net-sand-to-gross-shale ratio (NTG) and horizontal correlation lengths derived from well log data and observations of producing hydrocarbon fields in Southern Louisiana. We then performed an extensive suite of reservoir simulations of CO 2 injection and post-injection to evaluate the sensitivity of CO 2 plume migration and pressure response of the composite system to a series of geologic and fluid parameters including the lateral continuity of barriers, NTG, permeability anisotropy within the sand body, and capillary pressure contrast between the sand and shale facies. The results indicate that lateral continuity of barriers and NTG are the dominant controls on CO 2 plume geometry and pressure build-up in the reservoir, while the impact of NTG is particularly pronounced. The significance of intraformational barriers becomes apparent as they facilitate the local capillary trapping of CO 2 . Those barriers improve the pore space occupancy by promoting a more dispersed shape of the plume and ultimately retard the buoyancy-driven upward migration of the plume post injection.

58 GEOSCIENCES↗

Direct analysis of cotton swipes for plutonium isotope determination by microextraction-ICP-MS

This study demonstrates a method for determining the isotopic composition of low-level (sub-pg) plutonium (Pu) directly from a cotton swipe. Environmental sample (ES) swipes are routinely employed as a tool for monitoring activities in nuclear facilities. Traditional ES swipe analysis, as employed in nuclear safeguards, utilizes laborious ashing, digestion, and chemical separation procedures prior to mass spectrometric (MS) analysis. Here, an innovative sample introduction technique employing a microextraction probe to extract Pu directly from the swipe surface is described. The microextraction probe lowers onto the swipe surface, seals on a small area (8 mm 2 ), and delivers solvent (2% HNO 3 ) to extract actinide material that may be present. The extracted analyte is subsequently directed into a sector field inductively coupled plasma (ICP)-MS for isotope ratio determination. This microextraction-ICP-MS method successfully determined the isotopic composition ( 240 Pu/ 239 Pu and 242 Pu/ 239 Pu) of three Pu certified reference materials (CRM 136, 137, and 138) that were deposited (1 pg) onto ES swipes. The percent relative difference from the certified value, uncorrected for instrumental fractionation, was <2% for the 240 Pu/ 239 Pu ratio on all three CRMs and <10% for the 242 Pu/ 239 Pu ratio on CRM 136 and 138. Here, the percent relative standard deviation, an estimate of the sample-to-sample isotopic precision, was <4% for the 240 Pu/ 239 Pu and <15% for the 242 Pu/ 239 Pu. Method limits of detection were determined, based on measurements of an enriched 244 Pu material, to be ~7 fg. Additionally, a mixed uranium (U) and Pu deposition was made to determine the method's ability to simultaneously extract U and Pu and determine the isotopic composition of both analytes.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Synthesis and structural characterization of the new Zintl phases Eu 10 Mn 6 Bi 12 and Yb 10 Zn 6 Sb 12

Two new ternary compounds, Eu 10 Mn 6 Bi 12 and Yb 10 Zn 6 Sb 12 , were synthesized and structurally characterized. The synthesis was achieved either through reactions in sealed niobium tubes or in alumina crucibles by combining the elements in excess molten Sb. Their structures were elucidated using single-crystal X-ray diffraction, and they were determined to crystallize in the orthorhombic space group Cmmm (no. 65) with the Eu 10 Cd 6 Bi 12 structure type. Akin to the archetype phase, both Mn and Zn sites contain about 25% of vacancies. Furthermore, the anionic substructure of the title phases can be described as [M 6 Pn 12 ] (M = Zn, Mn; Pn = Sb, Bi) double layers composed of the corner and edge-sharing [MPn 4 ] tetrahedra, linked by [Pn 2 ] 4– dumbbells. Eu 2+ /Yb 2+ cations fill the space between the layers, with the valence electron counts adhering closely to the Zintl–Klemm rules, i.e., both Eu 10 Mn 6 Bi 12 and Yb 10 Zn 6 Sb 12 are expected to be valence-precise compounds. Analysis of the electronic structure and transport properties of Yb 10 Zn 6 Sb 12 indicate semimetallic behavior with relatively low Seebeck coefficient and resistivity that slightly decreases as a function of temperature.

36 MATERIALS SCIENCE↗

Polymorphism in A 3 MF 6 (A = Rb, Cs; M = Al, Ga) grown using mixed halide fluxes

Single crystals of A 3 MF 6 (A = Rb, Cs; M = Al, Ga) were grown from mixed alkali chloride/fluoride fluxes in sealed silver tubes. For Cs 3 AlF 6 and Cs 3 GaF 6 , two polymorphs were observed at room temperature: m-Cs 3 MF 6 and o-Cs 3 MF 6 . For the two Rb containing compositions, only one room temperature polymorph was observed: o-Rb 3 AlF 6 and t-Rb 3 GaF 6 , respectively. Simultaneous TGA/DSC and high temperature SCXRD/PXRD were used to study the high temperature behavior of A 3 MF 6 . Here, the compounds of all four compositions were found to undergo structure transitions upon heating to the same cubic structure type, c-A 3 MF 6 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The corrosion behavior of borosilicate glass in the presence of cementitious waste forms

Borosilicate glasses are widely used for radioactive waste disposal due to their ability to incorporate a variety of contaminants and radionuclides while exhibiting high durability in various disposal scenarios. This research evaluated the dissolution of borosilicate glass using both single-pass-flow-through (ASTM C1662-18) and product consistency test (ASTM C1285-21) methods with different solutions, including a cementitious-contacted water (called grout-contacted, GC, from this point) and solutions with varying levels of dissolved cementitious species such as Si, Ca, Al. Here, the results indicated that the presence of Ca plays a crucial role in suppressing glass corrosion, as evidenced by the slower normalized dissolution rates, which were one order of magnitude lower for boron and two orders of magnitude lower for rhenium, observed in both Ca-amended and GC solutions compared to the pH 12 buffer solution. This effect is attributed to the formation of a dense, low-porosity, and strongly bonded calcium silicate hydrate (CSH) layer on the glass surface, which implies that a glass corrosion process is influenced by ion exchange involving alkali ions Na + , K + , Ca 2+ , and hydrogen-containing species. A small number of glass particles treated in the GC solution showed minor corrosion pits in the form of shallow craters with an average diameter of approximately 500 μm. This observation is correlated with a significant reduction, 2000 to 3000 times lower, in the cumulative volume of glass pores, indicating that smaller pore voids were “sealed” in the presence of Ca 2+ ions, likely attributed to the formation of CSH precipitation or other corrosion products such as calcium carbonate saturated from the grout solution. These findings suggest that the presence of dissolved Ca in the GC solution can slow down the dissolution of borosilicate glass, contrary to the expected trend of higher dissolution rates resulting from exposure to high alkaline and thus higher pH solutions.

36 MATERIALS SCIENCE↗

In situ Raman investigation of Dy complexation in Cl-bearing aqueous solutions at 20–300 °C

Raman spectroscopy provides a versatile tool for in situ characterization of aqueous rare earth elements (REE) speciation at the molecular level. Complexation of REE with ligands such as Cl – and OH – is of particular interest for understanding the mobility of REE in NaCl-bearing hydrothermal fluids responsible for enriching REE to economic levels in nature. Raman spectroscopic studies of REE speciation in Cl-bearing aqueous fluids are primarily conducted at ambient temperature, whereas natural systems indicate temperatures of >100–600 °C. In this study, the speciation of Dy in acidic chloride-bearing hydrothermal solutions was investigated using confocal Raman spectroscopy with a new capillary Raman heating stage at 20–300 °C. Background solutions (pure water, NaCl-solutions) and solutions with 0.14–1.8 mol kg –1 dissolved DyCl 3 were sealed in quartz capillary cells. Comparison of the spectra for Dy chloride solutions with those for background solutions and the spectra for reference Dy-bearing solids was used to identify Raman bands specific to Dy–O and Dy–Cl bonds. The Raman band for the Dy–O stretching mode of hydrated Dy 3+ aqua ions was measured at 365–384 cm –1 and a Raman band for the Dy–Cl stretching modes of Dy chloride complexes was measured near 240 cm –1 . The Dy–O band decreases systematically with temperature, whereas the Dy–Cl band systematically increases, indicating a systematic increase in the stability of Dy chloride complexes with temperature. Here, this study provides the framework for expanding the use of in situ Raman spectroscopy to investigate the speciation of REE in aqueous solutions to hydrothermal conditions.

58 GEOSCIENCES↗

Cycloalkane-rich sustainable aviation fuel production via hydrotreating lignocellulosic biomass-derived catalytic fast pyrolysis oils

Sustainable aviation fuel (SAF) produced from lignocellulosic biomass is emerging as an ideal alternative to conventional jet fuel for aviation sector decarbonization. Catalytic fast pyrolysis (CFP) can convert lignocellulosic biomass into relatively stable bio-oil that can be selectively transformed to various transportation fuels through hydroprocessing under conditions of different severities. In this contribution, two CFP oils produced from pine-based feedstocks over different types of catalysts (i.e., ZSM-5 and Pt/TiO 2 catalysts) were hydrotreated at 125 bar in a non-isothermal process with a maximum temperature of 385 °C over a sulfided NiMo/Al 2 O 3 catalyst to produce SAF with high cycloalkane concentrations of 89–92 wt%. Cycloalkanes are an important component of jet fuel with advantageous fuel properties, such as high energy density, low sooting, and potential for replacing aromatic hydrocarbons to provide good seal swelling properties. The hydrotreating process successfully converted 91–92% of the biogenic carbon in the CFP oil intermediates to liquid-phase hydrotreated products. Through distillation, 39–40 wt% of the hydrotreated oils were collected in the jet-fuel range as SAF fractions. The rest of the hydrotreated product could be valorized as fuels (e.g., diesel) or chemicals. The SAF fractions with oxygen contents below the detection limit (<0.01 wt%) met ASTM D7566 finished fuel blend and D4054 Tier 1 specifications with respect to density, lower heating value (LHV), volatility, flash point, and freeze point. These results indicate hydrotreating lignocellulosic biomass-derived CFP oil as a promising pathway to produce high-quality SAF rich in cycloalkanes. Continued research is required to increase the SAF yield by process improvements, such as increased CFP oil yields, and an enhanced production of SAF-range molecules via e.g., cracking of high-molecular weight compounds either during CFP or hydrotreating, as well as evaluation of a broader range of jet fuel properties and performance requirements.

09 BIOMASS FUELS↗

Understanding the structural mechanics of ligated DNA crystals via molecular dynamics simulation

DNA self-assembly is a highly programmable method to construct arbitrary architectures based on sequence complementarity. Among various constructs, DNA crystals are macroscopic crystalline materials formed by assembling motifs via sticky end association. Due to their high structural integrity and size ranging from tens to hundreds of micrometers, DNA crystals offer unique opportunities to study the structural properties and deformation behaviors of DNA assemblies. For example, enzymatic ligation of sticky ends can selectively seal nicks resulting in more robust structures with enhanced mechanical properties. However, the research efforts have been mostly on experiments involving different motif designs, structural optimization, or new synthesis methods, while their mechanics are not yet fully understood. The complex properties of DNA crystals are difficult to study via experiments alone, and numerical simulation can complement and aid the experiments. The coarse-grained molecular dynamics (MD) simulation is a powerful tool that can probe the mechanics of DNA assemblies. Here, we investigate DNA crystals made of four different motif lengths with various ligation patterns (full ligation, major directions, connectors, and in-plane) using oxDNA, an open-source, coarse-grained MD platform. We found that several distinct deformation stages emerge in response to mechanical loading and that the number and the location of ligated nucleotides can significantly modulate structural behaviors. These findings should be useful for predicting crystal properties and thus improving the design.

DNA crystal↗

Hierarchical microstructure of Yb-filled skutterudites through ultrasonically atomized spherical powders for enhanced thermoelectric performance

Hierarchical microstructures are widely explored as a strategy to reduce lattice thermal conductivity in thermoelectric materials while preserving favorable electronic transport. Here we demonstrate that ultrasonic atomization of precursor powders provides an intrinsic pathway to generate such architectures in n-type Yb0.3Co4Sb12 skutterudites. Materials were synthesized by both conventional sealed-ampoule and ultrasonic atomization routes, each yielding essentially single-phase skutterudite after densification. However, the atomized spherical powders undergo a distinct reaction-driven microstructural evolution during thermal treatment prior to densification. Electron microscopy reveals that the skutterudite phase within the particles induces swelling, cracking, and fragmentation of the droplets before consolidation. Multimodal structural and microstructural characterizations show that densification of these fragmented powders produces a hierarchical microstructure consisting of submicron grains, micrometer-scale faceted crystallites, and powder-derived domains separated by oxide-decorated boundaries. Comprehensive thermoelectric transport measurements evidence that this multiscale architecture lowers the lattice thermal conductivity while maintaining favorable electronic transport, leading to an average ~10% enhancement in the thermoelectric figure of merit. Complementary 121Sb Mössbauer spectroscopy further indicates lattice softening in the atomized material. These results demonstrate that ultrasonic atomization provides an effective route to engineer hierarchical microstructures in skutterudite thermoelectrics and offers a promising strategy for tailoring thermal transport in energy-conversion materials.

Bouteiller, Hugo [ORNL] (ORCID:0009000421322962)↗

Extending Rucio with modern cloud storage support

Rucio is a software framework designed to facilitate scientific collaborations in efficiently organising, managing, and accessing extensive volumes of data through customizable policies. The framework enables data distribution across globally distributed locations and heterogeneous data centres, integrating various storage and network technologies into a unified federated entity. Rucio offers advanced features like distributed data recovery and adaptive replication, and it exhibits high scalability, modularity, and extensibility. Originally developed to meet the requirements of the high-energy physics experiment ATLAS, Rucio has been continuously expanded to support LHC experiments and diverse scientific communities. Recent R&D projects within these communities have evaluated the integration of both private and commercially-provided cloud storage systems, leading to the development of additional functionalities for seamless integration within Rucio. Furthermore, the underlying systems, FTS and GFAL/Davix, have been extended to cater to specific use cases. This contribution focuses on the technical aspects of this work, particularly the challenges encountered in building a generic interface for self-hosted cloud storage, such as MinIO or CEPH S3 Gateway, and established providers like Google Cloud Storage and Amazon Simple Storage Service. Additionally, the integration of decentralised clouds like SEAL is explored. Key aspects, including authentication and authorisation, direct and remote access, throughput and cost estimation, are highlighted, along with shared experiences in daily operations.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Design, Manufacturing, and Installation of DIII-D Lower Hybrid Current Drive Outer Wall Waveguides and Expandable Vacuum Interface

High field side lower hybrid current drive (HFS LHCD) is promising method for efficient, off axis current drive. To operate this system, development of an expandable combination radio frequency (RF) and vacuum interface was necessary to allow the long (~2 m) waveguides to thermally expand with respect to the DIII-D 0 degree R-1 port extension without damage to the waveguide or excessive force on the vacuum seals which was previously observed when baking the waveguides during operations that were installed in 2024. Design of a custom bellows assembly with RF feedthrough that allows >20mm of waveguide thermal expansion is presented. Fabrication of this bellows assembly required simultaneously vacuum brazing multiple 304 stainless steel flanges to an oxygen free high conductivity copper waveguide section which required significant manufacturing development.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

A path to scaling helium-3 spin-exchange optical pumping

Polarized 3 He has contributed to breakthroughs in particle physics, neutron scattering, and lung imaging, mostly by optical pumping of liter quantities in valved cells or in sealed cells pumped in situ. Only metastability exchange optical pumping currently meets the demand for delivering large quantities of highly polarized 3 He to external volumes. Our development program is under way to achieve medium to large-scale spin-exchange optical pumping of 3 He. Thin-walled aluminosilicate cells placed in contact with thermal reservoirs inside a pressure vessel were optically pumped with kilowatt-scale lasers spectrally narrowed to match pressure-broadened absorption linewidths. We report here the key elements of this program and significant milestones: multi-liter volume valved cells that provide long longitudinal lifetimes that reached polarization as high as 85% inside a thermally stable and pressurized environment.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Air-transfer production method for large-area picosecond photodetectors

We have designed and prototyped the process steps for the batch production of large-area micro-channel-plate photomultipliers (MCPPMT) using the “air-transfer” assembly process developed with single LAPPD TM modules. Results are presented addressing the challenges of designing a robust package that can transmit large numbers of electrical signals for pad or strip readout from inside the vacuum tube and of hermetically sealing the large-perimeter window–body interface. We have also synthesized a photocathode in a large-area low-aspect-ratio volume and have shown that the micro-channel plates recover their functionality after cathode synthesis. These steps inform a design for a multi-module batch facility employing dual nested low-vacuum and ultra-high-vacuum systems in a small-footprint. The facility design provides full access to multiple MCP-PMT modules prior to hermetic pinch-off for leak-checking and real-time photocathode optimization.

47 OTHER INSTRUMENTATION↗

An all-digital associated particle imaging system for the 3D determination of isotopic distributions

Associated particle imaging (API) is a non-destructive nuclear technique for the 3D determination of isotopic distributions. By detecting the alpha particle associated with the emitted neutron in the deuterium–tritium fusion reaction with a position- and time-resolving detector, the direction of the 14.1 MeV neutron and its time of emission can be determined. Employing this method, isotope characteristic gamma rays emitted in inelastic neutron scattering events can be correlated with the neutron interaction location. Here, an API system consisting of a sealed-type neutron generator, gamma detectors, and a position-sensitive alpha detector was designed, constructed, and characterized. The system was tested with common soil elements and shown to be sensitive to 12 C, 16 O, 28 Si, 27 Al, and 56 Fe. New aspects of our approach are the use of a yttrium–aluminum–perovskite scintillator, using a sapphire window instead of a fiber-optic faceplate for light transport to the photomultiplier, and the all-digital data acquisition system. We present a description of the system with simulations and experimental results that show a position resolution on the alpha detector of 1 mm, a depth resolution using a LaBr 3 detector of 6.2 cm, and an angular resolution of 4.5°. Additionally, we present single-element gamma response measurements for the elements mentioned above together with a comparison to Monte Carlo simulations (MCNP6).

47 OTHER INSTRUMENTATION↗

The design of a photoionization front experiment using the Z-Machine as a driving source and estimated measurements

Radiation-driven heat fronts are present in the early universe during reionization, the circumstellar medium of supernovae, and in high-energy-density physics experiments. Dedicated experiments to observe and diagnose the behavior of these types of heat fronts can improve our understanding of these phenomena. A simulation study of photoionization fronts using the HELIOS-CR radiation hydrodynamics code provides an experimental design for the Z-Machine at Sandia National Laboratory using a measurement-calibrated input radiation flux to drive the photoionization front. The simulations use detailed atomic physics and non-diffusive radiation transport in 1D to determine an optimal gas pressure of 0.75 atm for an experiment in N gas as well as the effects of increasing the thickness of the window that seals the gas cell. Post-processing of these simulations demonstrates that ratios of atomic rate coefficients place the heat front in a physics regime where photoionization dominates the energy deposition. Here, to see the sensitivity of the simulations to changes in the model and spatial grid, this analysis performed resolution, atomic model detail, and radiation transport angular grid studies showing less than 10% deviation from the nominal model for increased complexity, when possible. An effort to emulate 3D geometric effects on the radiation flux using an artificial attenuation scheme has shown that, even for conservative estimates of the flux, simulations still produce a photoionization front. Estimations of a streaked, visible spectroscopy measurement using SPECT3D showed that line emission measurements are present early in time and that later in time thermal emission should become dominant.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Sublimation temperature sensor for temperature locale

The sublimation temperature sensor (or “sublime sensor”) provides a continuum of measurement locations in which certain maximum temperatures are achieved during a heat up/cool down cycle. A predetermined material is encapsulated within a vacuum-sealed, non-volatile long tube (i.e., both ends capped and L$\gg$ D). This assembly is then inserted and centered into a heated zone, such as a furnace, exhaust pipe, or reactor. As the temperature increases, the material will sublimate (i.e., a process of having both the solid and gaseous states of matter simultaneously present) and will begin to fill the void - moving outward in both directions toward the ends of the tube. Once beyond the elevated temperatures, the gas will de-sublimate (i.e., deposition) onto the inner wall of the tube. The desired result of the sensor is the ring of material that develops over a relatively short period of time. This material deposit can be equated with temperature at an exact location. There is no need to interpolate and/or extrapolate for the desired measurement. Accuracy has been recorded for temperature locations on the range of ±2 mm over a 1 m span. Likewise, the precision of the measurement is ±0.2% the overall sensor domain. Furthermore, individual tubes with unique materials and pressures can be bundled together to provide a complete temperature profile of the heated zone.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗