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DOE OSTI2016

Effect of erodent particles on the erosion of metal specimens

This paper presents the experimental results of the measurement of erosion rate of carbon steel specimens in sand water slurry system in a slurry pot tester. Sylhet sand has been sieved to get three sizes of erodent particles; namely, less than 250 micron, 250 to 590 micron and 590 to 1190 micron. Experiments are done with three sand concentrations (10%, 15% and 20%). The rate of erosion of the carbon steel specimens is measured as the loss of weight per unit surface area per unit time under the dynamic action of solid particles. The eroded surfaces of the specimens are examined using Scanning Electron Microscopy (SEM) to visualize the impact of the slurry of various conditions. It is seen that irrespective of the particle size the rate of erosion increases with the increase of slurry concentration. This increment of erosion rate at high concentration is high for large particles. High erosion rate is observed in case of large sand particles. In case of small and fine particles erosion rate is small because of low impact energy as well as the wastage of energy to overcome the hindrance of the finer particles before striking on the specimen surface.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

DOE OSTI2012

Lands with Wilderness Characteristics, Resource Management Plan Constraints, and Land Exchanges: Cross-Jurisdictional Management and Impacts on Unconventional Fuel Development in Utah's Uinta Basin

Utah is rich in oil shale and oil sands resources. Chief among the challenges facing prospective unconventional fuel developers is the ability to access these resources. Access is heavily dependent upon land ownership and applicable management requirements. Understanding constraints on resource access and the prospect of consolidating resource holdings across a fragmented management landscape is critical to understanding the role Utah’s unconventional fuel resources may play in our nation’s energy policy. This Topical Report explains the historic roots of the “crazy quilt” of western land ownership, how current controversies over management of federal public land with wilderness character could impact access to unconventional fuels resources, and how land exchanges could improve management efficiency. Upon admission to the Union, the State of Utah received the right to title to more than one-ninth of all land within the newly formed state. This land is held in trust to support public schools and institutions, and is managed to generate revenue for trust beneficiaries. State trust lands are scattered across the state in mostly discontinuous 640-acre parcels, many of which are surrounded by federal land and too small to develop on their own. Where state trust lands are developable but surrounded by federal land, federal land management objectives can complicate state trust land development. The difficulty generating revenue from state trust lands can frustrate state and local government officials as well as citizens advocating for economic development. Likewise, the prospect of industrial development of inholdings within prized conservation landscapes creates management challenges for federal agencies. One major tension involves whether certain federal public lands possess wilderness character, and if so, whether management of those lands should emphasize wilderness values over other uses. On December 22, 2010, Secretary of the Interior Ken Salazar issued Secretarial Order 3310, Protecting Wilderness Characteristics on Lands Managed by the Bureau of Land Management. Supporters argue that the Order merely provides guidance regarding implementation of existing legal obligations without creating new rights or duties. Opponents describe Order 3310 as subverting congressional authority to designate Wilderness Areas and as closing millions of acres of public lands to energy development and commodity production. While opponents succeeded in temporarily defunding the Order’s implementation and forcing the Bureau of Land Management (BLM) to adopt a more collaborative approach, the fundamental questions remain: Which federal public lands possess wilderness characteristics and how should those lands be managed? The closely related question is: How might management of such resources impact unconventional fuel development within Utah? These questions remain pressing independent of the Order because the BLM, which manages the majority of federal land in Utah, is statutorily obligated to maintain an up-to-date inventory of federal public lands and the resources they contain, including lands with wilderness characteristics. The BLM is also legally obligated to develop and periodically update land use plans, relying on information obtained in its public lands inventory. The BLM cannot sidestep these hard choices, and failure to consider wilderness characteristics during the planning process will derail the planning effort. Based on an analysis of the most recent inventory data, lands with wilderness characteristics — whether already subject to mandatory protection under the Wilderness Act, subject to discretionary protections as part of BLM Resource Management Plan revisions, or potentially subject to new protections under Order 3310 — are unlikely to profoundly impact oil shale development within Utah’s Uinta Basin. Lands with wilderness characteristics are likely to v have a greater impact on oil sands resources, particularly those resources found in the southern part of the state. Management requirements independent of lands with wilderness characteristics far overshadow the challenges posed by wilderness issues. Wilderness character issues aside, a need to improve management integration remains. In researching past efforts to manage across the fragmented landscape we found that unilateral actions have been deeply divisive and engendered distrust among those impacted by the action. This distrust can linger for decades. Collaborative efforts, whether intended to protect lands, foster development, or do both, can represent an attractive alternative to unilateral action. Such collaborative efforts are more likely to succeed when they respond to strong incentives to act, evidence widespread involvement and support, and benefit from a committed champion. Projects are all but certain to fail where participants overreach or one of these elements is missing. For more than three decades, the state and federal government have cooperatively pursued land exchanges in order to “block up” isolated state trust lands and eliminate inholdings. These efforts can advance both conservation and development objectives, and are generally conducted in conjunction with efforts to protect extraordinary federal lands. Congress recognized the value of such exchanges and, as part of the Energy Policy Act of 2005, directed the Department of the Interior to pursue land exchanges as a means of facilitating environmentally responsible oil shale and oil sands recovery. But land exchanges are not without their challenges. Federal law requires equalizing the value of the lands and resources to be exchanged, and various means of equalizing value have been attempted. More flexible approaches have a higher likelihood of success, but are often criticized as resulting in an economic windfall for one party. Today challenges associated with appraisal and valuation stand as the most significant obstacles in the way of large-scale exchanges. Greater reliance on revenue sharing provisions that prevent an economic windfall to one party and avoid challenges inherent in valuing oil shale and oil sands resources may mark a promising path forward. The success or failure of these efforts could profoundly impact both the prospect of unconventional fuel development and wilderness character protection.

04 OIL SHALES AND TAR SANDS↗

DOE OSTI2025

Effect of CO 2 Concentration on the Microbial Activity of Orenia metallireducens (Strain Z6) in Surface Inert Materials

Carbon dioxide (CO 2 ) sequestration has garnered widespread attention as a key strategy for mitigating CO 2 emissions and combating the greenhouse effect. However, the mechanisms underlying the interactions between CO 2 , widespread siliceous minerals and biological processes remain unclear. The present study explored the potential impacts of different CO 2 concentrations on microbial activity, environmental conditions and their feedback on the fate of CO 2 . A total of 20 experimental conditions was created, with the variables including different natural and synthetic siliceous minerals (e.g., quartz sand and a type of commercial glass beads), the presence or absence of the iron-reducing microorganism Orenia metallireducens (strain Z6) and varying CO 2 concentrations (0%, 20%, 50%, 100%) in the presence of ferrihydrite and pyruvate. Geochemical, microbial and mineralogical analyses revealed that elevated CO 2 concentrations significantly inhibited microbial Fe(III) reduction and pyruvate metabolism. Interestingly, compared to cultures without mineral amendments or those with glass beads alone, the addition of quartz sand enabled strain Z6 to better withstand the environmental stress caused by elevated CO 2 , promoting pyruvate fermentation and iron reduction. In addition to an increased pH, the formation of siderite, hematite and vivianite was also observed in the bioactive systems. Although both glass beads and quartz sand were primarily composed of silica, differences in the mineral structure, elemental composition and acid neutralization capacity rendered quartz sand more chemically active and unexpectedly led to greater CO 2 sequestration.

CO2 stress↗

DOE OSTI2019

The Development of Legacy Waste Scaling Factors for Radioactively Contaminated Soils at Chalk River Laboratories - 19333

The Chalk River Laboratories (CRL) began nuclear operations in 1947. Beginning in 1952 after the NRX accident, the management of excess contaminated liquids from the accident, and later in 1953, other waste liquids, were intermittently dispersed to trenches and pits in the local sand. The local sands proved effective at immobilization of actinides, and most activation and fission products. However there was very limited retention of some more commonly mobile radionuclides. Sand filtration performance and radionuclide migration was studied beginning in 1952. Monitoring data indicated slow migration of most radioactive contaminants away from the trenches and pits due to the adsorbing capacity of the sand substrate. The radionuclide migration continues to be studied today in frequent plume monitoring studies. Because many hard-to measure (HTM) radionuclides may also present as long term dose contributors in post remediation scenarios, or in disposal site performance assessments, the quantification of these HTM radionuclides is important. The use of scaling factors between HTM radionuclides and easy-to-measure (ETM) radionuclides (gamma emitters) for packaged soil wastes would alleviate significant effort in sampling individual waste containers. As part of plume monitoring studies and the environmental remediation process, significant characterization of soils have been performed at the site. The soil sample data from multiple historic waste management areas across site is combined and relationships between HTM radionuclides and ETM or key radionuclides are examined. Additional (secondary) relationships between ETM key nuclides are also explored to evaluate secondary scaling relationships between ETM key radionuclides (e.g., Co- 60/Cs-137), because of the significant decay of the activation product key radionuclide Co-60, (predominantly 10-20 half-lives). The evaluation is yielding consistent scaling factors for legacy soil wastes in the historic waste management areas. Given the hydrogeology of the site, a sandy shallow unconfined aquifer, and the annual precipitation of about 0.85 m/a, this evaluation reveals some expected relationships between fission products and actinides and some unanticipated relationships between more mobile radionuclides and key gamma emitters. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2015

Electrical properties of methane hydrate + sediment mixtures: The σ of CH 4 Hydrate + Sediment

Knowledge of the electrical properties of multicomponent systems with gas hydrate, sediments, and pore water is needed to help relate electromagnetic (EM) measurements to specific gas hydrate concentration and distribution patterns in nature. We built a pressure cell capable of measuring in situ electrical properties of multicomponent systems such that the effects of individual components and mixing relations can be assessed. We first established the temperature-dependent electrical conductivity (σ) of pure, single-phase methane hydrate to be ~5 orders of magnitude lower than seawater, a substantial contrast that can help differentiate hydrate deposits from significantly more conductive water-saturated sediments in EM field surveys. We report σ measurements of two-component systems in which methane hydrate is mixed with variable amounts of quartz sand or glass beads. Sand by itself has low σ but is found to increase the overall σ of mixtures with well-connected methane hydrate. Alternatively, the overall σ decreases when sand concentrations are high enough to cause gas hydrate to be poorly connected, indicating that hydrate grains provide the primary conduction path. Our measurements suggest that impurities from sand induce chemical interactions and/or doping effects that result in higher electrical conductivity with lower temperature dependence. Finally, these results can be used in the modeling of massive or two-phase gas-hydrate-bearing systems devoid of conductive pore water. Further experiments that include a free water phase are the necessary next steps toward developing complex models relevant to most natural systems.

03 NATURAL GAS↗

DOE OSTI2018

Numerical simulations of depressurization-induced gas production from an interbedded turbidite gas hydrate-bearing sedimentary section in the offshore India: Site NGHP-02-16 (Area-B)

The recent National Gas Hydrate Program Expedition 02 (NGHP-02) identified the existence of gas hydrate-bearing sand reservoirs at a number of sites in the offshore of India including Site NGHP-02-16 in Area-B of the Krishna-Godavari Basin. The architecture of that gas hydrate accumulation is characterized by thin, gas hydrate-bearing, high quality sand layers interbedded with mud layers within a turbidite sedimentary interval. The lowest gas hydrate-bearing layer contacting a thinly-interbedded saline aquifer designates the base of the gas hydrate stability zone (BGHSZ). The proximity of the BGHSZ and the average temperature around 20 °C make the reservoir a favorable target for hydrate destabilization by means of the depressurization method. The results of the reservoir simulations indicate high gas production potential from this marine gas hydrate deposit with manageable concomitant water production using a well completion design that hydraulically isolates layers with water-saturated sands. Using a detailed geological input model, the predicted cumulative gas rates reach ~3.1 × 10 4 m 3 /day (~1.1 MMscf/day) after 90 days of continuous depressurization and demonstrate sustained production rates ~3.0 × 10 4 m 3 /day (~1.0 MMscf/day) after 5 years of production. The interbedded nature of this gas hydrate occurrence promotes the development of horizontal dissociation interfaces between gas hydrate-bearing sand and mud layers. As a result, non-uniform gas production along the horizontal interfaces becomes a primary determinant of reservoir performance. Simulation cases have been executed to determine the impact of the uncertainty in in situ reservoir permeability and the manner in which intrinsic permeability dynamically changes during dissociation in response to the imposed effective stress increase. Here, the cases based on low initial effective permeability and high sensitivity of compaction to stress result in the least favorable production predictions.

58 GEOSCIENCES↗

DOE OSTI2013

Environmental and technical assessments of the potential utilization of sewage sludge ashes (SSAs) as secondary raw materials in construction

Highlights: ► We used sewage sludge ashes in ready-mix concrete recipe. ► SSAs were used as a substitution of cement. ► Compressive strength of ready-mix concrete incorporating SSAs were similar as blank one. ► Contaminants leaching from concrete monoliths were above threshold limits. - Abstract: Ashes produced by thermal treatments of sewage sludge exhibit common properties with cement. For example, major elements present in SSA are the same of major elements of cement. Hydraulic properties of SSA are quite the same of cement ones. They may therefore be used to substitute part of cement in concrete or other cementitious materials, provided that technical prescriptions are satisfied and that environmental risks are not significantly increased. The objective of the present study was to determine the appropriate substitution ratios to satisfy both technical and environmental criteria. In a first step, the elemental composition and particle size distribution of the ashes were measured. Then the ashes were used along with Portland cement and sand at different ratios of substitution to produce mortar and concrete which were cured for up to 90 days into parallelepipedic or cylindrical monoliths. The mechanical properties of the monoliths were measured using standard procedures for flexural and compressive strengths, and compared to blanks containing no ashes. The environmental criteria were assessed using leaching tests conducted according to standard protocols both on the ashes and the monoliths, and compared to the blanks. Results showed that the characteristics of the ashes ranged between those of cement and sand because of their larger particle size and higher content in SiO{sub 2} as compared to cement. The monoliths made with the highest substitution ratios exhibited a significant decrease in flexural and compressive strengths. However, when the ashes were used in partial substitution of cement at appropriate ratios, the concrete monoliths exhibited similar compressive strengths as the blank samples. The most appropriate ratios were found to be 10% substitution of cement and 2% substitution of sand. The leaching tests conducted on the ashes in their powdery form revealed that amongst the potential contaminants analyzed only Mo and Se were leached at concentrations above the threshold limits considered. The leaching tests conducted on concrete monoliths showed however that none of the contaminants monitored, including Mo and Se, were leached above the limits. In addition, whether concrete recipe incorporated ashes or not, similar concentrations were measured for each potential contaminant in the leachates. This result indicated that mixing ash with cement and sand to produce mortar or concrete induced a stabilization of Mo and Se and thereby constituted in itself a good treatment of the ashes.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2023

Selecting the Optimal Fluorinated Ether Co-Solvent for Lithium Metal Batteries

To guide the selection of a suitable fluorinated ether (FE) co -solvent for lithium metal batteries, it is crucial to understand the relationship between the organic structures of the FEs and the electrochemical performance of an FE-containing electrolyte. In this work, 1,1,2,2-tetrafluoro-1-(2,2,2-trifluoroethoxy)ethane (FEE), 1,1,2,2-tetrafluoro-3-(1,1,2,2-tetrafluoroethoxy)-propane (TTE), and 1,2-bis(1,1,2,2-tetrafluoroethoxy)ethane (OFDEE) were chosen as representative FE co-solvents because of their distinct structural properties. The structure-activity relationship between the FEs and the electrochemical performance of Li||LiNi 0.6 Mn 0.2 Co 0.2 O 2 (Li||NMC622) cells was correlated and quantified by Fourier-transform infrared and multi-dimensional nuclear magnetic resonance techniques. Sand's model was also employed to assess the extent of lithium dendrite formation in the cells using various FE electrolytes. The cycling performance of Li||NMC622 cells using different FE co-solvents follows the order FEE > TTE > OFDEE. Further, since the direct measurement of Sand's time is difficult, we introduced relative Sand's time to probe the diffusion behavior of each electrolyte, and the results showed that the best performance was obtained in the electrolyte with the longest relative Sand's time. Moreover, the lithium metal cell using the electrolyte with FEE co-solvent showed similar capacity retention compared with the baseline electrolyte at room temperature, but it demonstrated significantly improved low-temperature performance. The results indicate that FEE is a promising co-solvent candidate for improving the low-temperature performance of lithium metal batteries because it possesses not only non-solvating behavior but also very low viscosity and non-flammability. The advanced electrolyte LiPF 6 -FEC-DMC-FEE enables very stable cycling of lithium metal batteries at various temperatures.

25 ENERGY STORAGE↗

DOE OSTI2026

Dominant Controls on Preferential Flow and Their Implications for Future Soil Water Fluxes

Abstract Soil water flow, particularly preferential flow (PF), is a critical control on hydrological and biogeochemical processes, including groundwater recharge, contaminant transport, and carbon cycling. However, it remains challenging to predict PF occurrence across large environmental gradients. Here, we developed a deep learning (DL) model to estimate event‐scale soil water flow velocity and the probability of PF occurrence using high‐frequency soil moisture and precipitation data from 33 sites across the National Ecological Observatory Network. The model demonstrated high skill in predicting the binary occurrence of PF (91% F1‐score; 85% accuracy) but the performance was limited in predicting soil water velocity ( R 2 = 0.31). We found that precipitation characteristics (duration, volume, and intensity) were the most important predictors for soil water velocity. Among the non‐precipitation event variables, sand content showed relatively high predictive skill, though differences among non‐event climate variables were generally modest. Lower sand content was associated with increased predicted soil water velocity, a finding that highlights the role of soil structure in producing more non‐uniform flow, which contrasts with traditional uniform flow models. Projecting a reduced DL model under both moderate and high‐emissions future climate scenarios (2060–2099 Representative Concentration Pathways 4.5 and 8.5), we found ∼7.3% increase under RCP4.5 and ∼15% under RCP8.5 of soil water velocities compared to the historical simulation, while modeled likelihood of PF changed little. These findings suggest climate change is not making PF more frequent, but it is making existing PF pathways more efficient with important consequences for associated nutrient and contaminant transport under climate change. Plain Language Summary Water movement in soil is critical for water quality. While often modeled as a uniform flow process, in reality water moves rapidly through cracks and burrows in what is called “preferential flow” (PF), which limits natural filtration and can transport pollutants. We developed a deep learning model, trained on data from 33 U.S. sites, to predict when and how fast this PF occurs based on precipitation, soil, and climate data. The model showed that precipitation characteristics (duration, intensity, volume) were the most important predictors of PF. Lower soil sand content/higher clay content was associated with faster water flow, likely due to clay soils forming aggregates and cracks that water moves through rather than infiltrating uniformly. Further analyses based on climate projections suggest that the speed at which PF occurs will become more rapid under future climate scenarios compared to historical simulation. This highlights the need to represent PF in soil water models when assessing future water quality. Key Points The effect of precipitation peak intensity on soil water velocities declined with increasing precipitation intensity Antecedent soil moisture failed to predict preferential flow (PF), contrasting the high predictive power of sand content Climate predictions suggest that soil water velocities through PF paths will increase ∼15% by 2099

Li, Bonan↗

DOE OSTI2018

Analysis and Distribution of Proppant Recovered from Fracture Faces in the HFTS Slant Core Drilled through a Stimulated Reservoir

Although sand proppant has been used since 1949 to increase efficacy of hydraulically fractured treatments by preventing fractures from closing after well depressurization, many questions remain regarding the behavior and distribution of proppant in the subsurface. To this end, we quantified the amount of recovered proppant in open fractures within a slant core drilled through hydraulically fractured Wolfcamp Shale. To improve understanding of hydraulic-fracture growth and patterns, we then addressed basic questions such as the following regarding proppant behavior in the subsurface: Is there variation along the length of the examined core? Is the proppant mainly found in hydraulic fractures, in reactivated natural fractures, or is it transported into drilling-induced fractures during recovery? Do the majority of proppant grains remain whole or tend to get crushed? To answer these questions, we collected all material from every open fracture (407 samples total) within ~600 ft of core. Samples consisted of drilling mud, aluminum shavings from the core barrel, shale and lithic fragments, calcite, and, potentially, sand proppant (95% plain and 5% colored resin-coated grains) pumped during the hydraulic fracturing of adjacent wells. We then washed, sieved into four size fractions, weighed, and imaged all samples for quantitative image analysis. Retrieved samples were labeled with respect to a master fracture database, where fractures were identified in the core and on CT scans of each 3-ft interval, allowing us to code them as either hydraulic, natural reactivated, or drilling/recovery-induced fractures. From this coding, we quantified the amount of proppant within each fracture, analyzed the distribution of grains among different fracture types, and traced base versus colored grains. Proppant packs 0.5–1 cm thick were found in two locations where there was complex fracture geometry, but fracture faces showed no evidence of proppant embedment. In situ sand patches were found on a few fracture faces, mostly in fractures near the proppant packs. Pumped proppant was 100 and 40/70 mesh (149–420 μm), and even though widespread grain crushing is not observed, the majority of recovered proppant ranges from 63 to 250 μm. The distribution of retrieved proppant, especially the larger retrieved sizes (250– >500 μm), mirrors the proximity of the slant core to the hydraulic fracture treatment wells. Hydraulic fracture samples contained variable amounts of proppant, and natural reactivated fractures sometimes contained more proppant than nearby hydraulic fractures, suggesting transference between fracture types in the subsurface. Regarding colored proppant, some colored sands occurred in discreet fractures, whereas other colors appeared to be mixed and widespread. Ultimately, all fractures contain at least some proppant, especially in the smallest size fractions; however, the extent to which the proppant was introduced during the core-drilling process is still unknown. Our study is one of the first attempts at physically recovering and quantifying injected proppant from parted fracture breaks within a stimulated reservoir, and the results are significant in terms of understanding propped fracture networks and predicting future proppant distribution during hydraulic fracturing.

Elliott, Sara↗

DOE OSTI2013

Assessing Uncertainty and Repeatability in Time-Lapse VSP Monitoring of CO2 Injection in a Brine Aquifer, Frio Formation, Texas (A Case Study)

This study was done to assess the repeatability and uncertainty of time-lapse VSP response to CO 2 injection in the Frio formation near Houston Texas. A work flow was built to assess the effect of time-lapse injected CO 2 into two Frio brine reservoir intervals, the ‘C’ sand (Frio1) and the ‘Blue sand’ (Frio2). The time-lapse seismic amplitude variations with sensor depth for both reservoirs Frio1 and Frio2 were computed by subtracting the seismic response of the base survey from each of the two monitor seismic surveys. Source site 1 has been considered as one of the best sites for evaluating the time-lapse response after injection. For site 1, the computed timelapse NRMS levels after processing had been compared to the estimated time-lapse NRMS level before processing for different control reflectors, and for brine aquifers Frio1, and Frio2 to quantify detectability of amplitude difference. As the main interest is to analyze the time-lapse amplitude variations, different scenarios have been considered. Three different survey scenarios were considered: the base survey which was performed before injection, monitor1 performed after the first injection operation, and monitor2 which was after the second injection. The first scenario was base-monitor1, the second was basemonitor2, and the third was monitor1-monitor2. We considered three ‘control’ reflections above the Frio to assist removal of overburden changes, and concluded that third control reflector (CR3) is the most favorable for the first scenario in terms of NRMS response, and first control reflector (CR1) is the most favorable for the second and third scenarios in terms of NRMS response. The NRMS parameter is shown to be a useful measure to assess the effect of processing on time-lapse data. The overall NRMS for the Frio VSP data set was found to be in the range of 30% to 80% following basic processing. This could be considered as an estimated baseline in assessing the utility of VSP for CO 2 monitoring. This study shows that the CO 2 injection in brine reservoir Frio1 (the ‘C’ sand unit) does induce a relative change in amplitude response, and for Frio2 (the ‘Blue’ sand unit) an amplitude change has been also detected, but in both cases the uncertainty, as measured by NRMS indicates the reservoir changes are, at best, only slightly above the noise level, and often below the noise level of the overall data set.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2016

2015 Advanced Site Investigation and Monitoring Report Riverton, Wyoming, Processing Site September 2016

The U.S. Department of Energy conducted initial groundwater characterization of the Riverton, Wyoming, Processing Site in the 1990s. The characterization culminated in a Site Observational Work Plan in 1998 that recommended a natural flushing compliance strategy. Results of verification monitoring indicated that natural flushing was generally progressing as expected until June 2010, when significant increases in contaminant concentrations were measured in several monitoring wells downgradient of the site after the area flooded. In response to the unexpected results following the flood, an enhanced characterization of the surficial aquifer was conducted in 2012, which included installation of 103 boreholes along nine transects with a Geoprobe, collection of 103 water samples and 65 soil samples, laboratory tests on the soil samples, and additional groundwater modeling. This advanced site investigation report summarizes additional investigation in 2015 through the use of backhoe trenching, sonic drilling, multilevel monitoring wells, direct-push drilling, and temporary well points to collect soil and groundwater samples. Additional surface water measurements were made included the installation of a stilling well and the measurement of stream elevation along the Wind River to approximate upgradient groundwater heads. Groundwater sampling included the addition of geochemical constituents and isotopes that have not been sampled in the past to better understand post-flood conditions and the possibility of additional or ongoing contaminant sources. This sampling was performed to (1) better define the contaminant plumes, (2) verify the occurrence of persistent secondary contaminant sources, (3) better understand the reason for the contaminant spikes after a 2010 flood, and (4) assess contaminant plume stagnation near the Little Wind River. This report provides data analyses and interpretations for the 2015 site investigation that addresses these issues and provides recommendations for future efforts. Observations from trenches and sonic drilling indicate the general lithology of the shallow, unconsolidated sediments consists of a silt zone at the surface that ranges from 2.5 to 4.8 feet below ground surface, underlain by sand and gravel, underlain by the top of the weathered bedrock (Wind River Formation). Soil data from trenches and sonic drilling indicate (1) elevated concentrations of several constituents in the silt zone, likely due to the formation of evaporites, (2) uranium is the only measured element that appears to be concentrated in the silt over the groundwater contaminant plume, (3) in the former tailings impoundment area, there may be a thin unsaturated zone with elevated uranium in the native material just below the fill, (4) in the former tailings impoundment area, slightly higher uranium concentrations occur in the underlying saturated sand and gravel, and (5) several bedrock samples have a unique geochemical signature, generally related to a higher silt content. Assessment of groundwater flow included measuring river elevations along the Wind River and installing the temporary well points adjacent to the Little Wind River that provided additional data points to refine contours for water table elevations. These data confirm past interpretations of groundwater flow to the southeast across the site toward the Little Wind River. Hydraulic head elevations between paired surficial and semiconfined aquifer wells indicate variable vertical gradients across the site with the potential for upward and downward flow. Additional direct-push drilling and groundwater sampling confirmed the contaminant plume configuration, but it also revealed a low-sulfate-concentration zone at the edge of the former tailings impoundment. Temporary well points provided better definition of plume concentrations at the bank of the Little Wind River, and data from these wells indicate plume discharge to the river. Additional sampling in an area southwest of the plume that had elevated uranium groundwater concentrations in the past did not have any uranium concentrations above the U.S. Environmental Protection Agency maximum concentration limit for uranium. Results from multilevel monitoring wells indicate some geochemical differences with depth, but overall concentrations are similar to those in nearby conventional monitoring wells in the long-term monitoring program. Geochemistry data from these multilevel monitoring wells confirm the general increase in contaminant concentrations toward the river and toward the plume centerline for chloride, sulfate, and uranium but highlight geochemical controls on calcium. Iron data indicate slightly reducing conditions, especially near water table and bedrock surfaces, with more oxidizing conditions in the middle of the sand and gravel. Uranium activity ratios (234U/238U) confirm the uranium plume in the surficial aquifer as being mill related, and the area to the southwest outside the plume as natural, non-mill related. In the semiconfined aquifer, evidence of aquifer connection and impacts from the mill is inconclusive. Values of δD and δ 18 O suggest water is derived from different sources and tritium data confirm that the semiconfined aquifer water is generally older than the surficial aquifer water. However, these data do indicate some groundwater communication from the surficial aquifer into the semiconfined aquifer, which resulted in δD and δ 18 O and tritium values in the semiconfined aquifer that are more similar to those in the surficial aquifer. Values of δ 34 S sulfate in the semiconfined aquifer combined with sulfate concentrations indicate the potential for some mill- related sulfate in the semiconfined aquifer, albeit limited to an area near and beneath the former tailings impoundment. Uranium and molybdenum concentrations in the semiconfined aquifer are below groundwater standards in all wells. However, the elevated molybdenum concentrations at one semiconfined aquifer well underneath the former tailings impoundment suggests a mill- derived source for the uranium and molybdenum in that well. It is possible that aquifer cross- communication occurred when the tailings impoundment was active and created a higher head. Current cross-communication appears unlikely given the large differences in tritium values and an upward hydraulic head at this location. Nine domestic wells are located within the institutional control boundary (eight in the confined aquifer and one in the semiconfined aquifer). Uranium and molybdenum concentrations in all samples collected from these wells were one or two orders of magnitude below the groundwater standards. Surface water flow in the Little Wind River in September 2015 was low compared to historical averages for that time of year. As a result, the uranium concentration measured in the Little Wind River was at a historical maximum at the sampling location upstream of the site. However, the impact of uranium discharge from the groundwater plume into the Little Wind River was not measureable. Elevated sulfate concentrations were observed in an outfall ditch related to an active sulfuric acid plant. Uranium concentrations in the oxbow lake remain at concentrations above the groundwater standard. Plume contaminant concentrations had returned to levels found prior to the 2010 flood by the end of 2015. However, these concentrations still exceed model predictions for natural flushing, and the current data indicate that natural flushing to achieve remediation goals within the 100-year time period is not likely, especially with the high potential for additional floods in the update to the conceptual site model (CSM), soil data indicate additional contaminant sources, specifically uranium, in evaporites within the silt layer over the uranium plume and in naturally reduced zones (NRZs). Additional zones of slightly elevated uranium concentration are in the native sediments just above the water table but below the fill layer in the former tailings impoundment area. This area also has slightly elevated uranium in the sand and gravel below the water table. Mass balance calculations indicate that small amounts of dissolution in any of these zones with increased uranium in the solid phase can produce groundwater uranium concentrations above the groundwater standard and could account for the post-flood uranium spike. The additional uranium near the former tailings impoundment provides a mechanism for a continuing source for the uranium plume that was not considered in earlier natural flushing models. In addition, uranium released from the silt layer or the NRZs seasonally and during flooding may add uranium to the groundwater plume near the Little Wind River. These mechanisms provide a possible explanation for plume persistence, along with spikes in concentrations during floods, that creates the current plume configuration. Additional updates to the CSM include (1) chloride flushes more rapidly than uranium beneath the former mill site, (2) chloride in the silt layer provides a scenario in which chloride cannot be used as a conservative tracer (especially in areas prone to flooding), (3) uranium concentrations with depth can be variable (especially below NRZs), and (4) calcite and gypsum solubility limits appear to provide important geochemical controls on groundwater geochemistry. The conclusion of this study provides several recommendations for additional work to refine the CSM and continue assessment of the natural flushing compliance strategy. Recommendations for additional work include targeted soil and groundwater sampling to assess geochemical conditions, distribution of contaminants, and groundwater/surface water interaction; additional column tests to provide data for geochemical modeling; and development of an updated groundwater flow model, which will be used in conjunction with a geochemical model to assess the viability of the natural flushing compliance strategy.

2015 Monitoring Riverton, WY↗

DOE OSTI2018

Mechanisms for Methane Transport and Hydrate Accumulation in Coarse-Grained Reservoirs

The distribution of natural methane hydrate within high saturation reservoirs and mechanisms that control the migration of methane are an active area of research. In this project, we studied methane migration mechanisms and associated hydrate accumulation rates in coarse-grained sands of the Terrebonne Basin, located in Walker Ridge Block 313 (WR313), northern Gulf of Mexico. Hydrate in this area is distributed heterogeneously within ~900 m of methane hydrate stability zone, in both thick (10-25 m) and thin (< 3 m) sand layers, and in units of subvertical hydrate-filled fractures. We investigated hydrate formation from diffusively and advectively supplied methane using one-, two-, and three-dimensional basin modeling with inputs from well log and seismic data. The hydrate accumulations at WR313 can mostly be explained by short, diffusive migration of methane as well as short-range advective transport of methane from clays into neighboring coarser-grained layers. This is likely enhanced by small-scale lithologic variations, including local microbial methanogenesis in interbedded clays. Furthermore, our work shows overpressure in clay sediments surrounding sand reservoirs may enhance short-range diffusive migration. Long-range migration of dissolved methane and gas mainly influence hydrate saturation right at the base of the hydrate stability zone, although the dissolved phase can be channeled upwards along sands by compaction-driven flow. Capillary effects can allow gas bubbles to migrate appreciable distances above the predicted base of gas hydrate stability, possibly reaching a few tens of meters into the hydrate stability zone. Recycling methane from hydrate buried beneath the base of the hydrate stability zone can concentrate hydrate at large saturations within a few tens of meters of the base of hydrate stability.

58 GEOSCIENCES↗

DOE OSTI2018

Prototyping and Manufacturing of Magnetic Gearbox Components using Innovations in Castings

This project combines additive manufacturing with the broadly deployed practice of metal casting. Combining these methods will unlock new design possibilities while reducing the economic burden of early stage prototyping while leveraging well established high throughput sand casting. Two main approaches are evaluated: direct printing of single use sand molds and printing of reusable impression patterns used to create sand molds. Reusable impression molds typically can be used to produce hundreds to several thousands of casting thereby amplifying the function of the 3D printed replica mold. Emrgy’s newly developed and tested proprietary magnetic gearbox system for low head hydroelectricity generation was the subject part of this study. Leveraging ORNL’s additive manufacturing capability and expertise, a pattern impression was produced and used to create multiple sand molds of the gearbox during phase 1. Even before considering the cost savings possible once rigging and pattern mounting is optimized through repetition and improved design, final part costs using this combined method resulted in an 80% cost reduction over EMRGY’s previous method of subtractive manufacturing for gearbox production.

36 MATERIALS SCIENCE↗

DOE OSTI2020

Characterization of Carbon Sequestration Targets of the Mid-Atlantic Coastal Plain and Adjacent Offshore Region

Lower to mid-Cretaceous age rock formations were identified on the onshore Mid-Atlantic U.S. Coastal Plain and offshore northern Baltimore Canyon Trough (BCT) that show great potential as reservoirs for carbon sequestration. These targets are constrained using a sequence stratigraphic approach by integration of multi-channel seismic, geophysical well-log, core, and biostratigraphic datasets. In the onshore coastal plain of New Jersey, Delaware, and Maryland, the Lower Cretaceous Waste Gate Formation and mid-Cretaceous Potomac Formation/Group were divided into three major sequences (Waste Gate-Potomac Unit I, Potomac Unit II, and Potomac Unit III). The analysis concluded that Waste Gate-Potomac Unit I sequence is most suitable for carbon storage, as it has thick, correlatable sands in New Jersey and Maryland that are well confined in New Jersey, and could store potentially large volumes of CO2 (~ 8-34 Gt). In the offshore, we evaluate the mid-Cretaceous Logan Canyon Formation which we divide into three sequences (LC3, LC2, and LC1). All three sequences show potential for large volumes of CO2 storage (~5.9 Gt on the Great Stone Dome (GSD); preliminary volume estimates in the MRCSP ATLAS are currently being updated by MAOCSRAP). The Logan Canyon Sands are an excellent target for carbon storage in the offshore Baltimore Canyon Trough; they are thick, correlatable sands with high permeabilities and porosities, and are confined by the thick Dawson Canyon Shale. Sands are particularly thick, porous, and very permeable in wells on the GSD, which provides a great structural trap, and as such is a world-class target for carbon sequestration.

01 COAL, LIGNITE, AND PEAT↗

DOE OSTI2024

DECOVALEX-2023: Task D Final Report

Task D of DECOVALEX-2023 is focused on the simulation of the coupled thermal hydraulic-mechanical (THM) behaviour in the full-scale engineered barrier system (EBS). The Horonobe EBS experiment is the demonstration of the full-scale EBS in the underground research laboratory (URL) (performed by JAEA in the Horonobe URL in Japan). Task D consisted of the three steps, a preliminary step (Step 0), simulation of the laboratory tests (Step 1) and simulation of the in-situ full-scale EBS experiment (Step 2). Since the Horonobe EBS experiment demonstrates the vertical emplacement option of the EBS, the experiment gallery is also backfilled with the backfill material. Therefore, interaction between the EBS and the backfill material can also be demonstrated, such as deformation (change of density) of the buffer material. The underground water in the Horonobe URL is saline. This fact adds chemical processes to THM behaviour. For example, mechanical properties (such as swelling pressure of the buffer material and backfill material) and hydraulic properties (such as permeability of the buffer material and backfill material) change depending on the water chemistry. Task D was therefore a challenging Task focused on not only the relatively simple THM behaviour but also complex THM behaviour including chemical processes. Six research teams (BGR, CAS, JAEA, KAERI, SNL and Taipower) participated the Task D. BGR, CAS, JAEA, KAERI and Taipower research teams selected a THM approach, while the SNL research team selected a TH approach. Step 1 involved the simulation of laboratory test results and was important to check the numerical codes developed by the research teams. Step 1 was divided into four sub steps. The simulation results through the Step 1 identified the parameters for simulation of the Step 2. Basic parameters of the materials (buffer material, backfill material, rock mass, concrete, sand) were provided by JAEA. Special parameters which research team needed were identified by back analysis of Step 1. Most notably the mechanical behaviour of swelling and displacement depended on the applied model (elastic model or elastoplastic model). Parameters such as Young’s modulus were found to need smaller values than characterised in the fundamental laboratory test results (Step 1-1, 1-2) for the elastic model. Although laboratory experiments are usually simple, test results contained some error. For example, if the saturation level is 100 % or higher, it should be considered an error. This situation was presented in the Step 1-3. A possible reason is that the buffer material is a mixture of bentonite and silica sand. When a specimen is cut to measure volume or weight, sand grains will affect the measurement data. In Step 2, boundary conditions such as temperature on the surface of the simulated overpack, heater power of the electrical heaters installed in the simulated overpack, injection pressure and inflow rate of the test water, were applied. The outer boundary conditions can be selected using measured data (injection pressure and inflow rate of the test water that is controlled by the injection systems installed in the sand layer around the buffer material and in the boundary between backfill material and concrete support). Since such measured data has some noise, research teams developed their own simplified boundary conditions. Inner boundary conditions can be selected using measured data as heater power and temperature on the surface of the simulated overpack. These data also contain some noise, so research teams developed their own simplified developed boundary conditions. Task D validated various approaches thorough the simulation of the in-situ full scale EBS system including backfill of the gallery: variations in the coupling processes (THM or THC), analysis codes, and boundary conditions. Temperature distribution in the buffer material was simulated well by all research teams. This means thermal behaviour is not sensitive to the simulation approaches. Although the water content distribution on the outside of the buffer material was well simulated by all research teams, the simulation results differ from the measured values inside the buffer material (at the centre and inside, near the simulated overpack). The buffer material is made from tap water, but in the in-situ experiment, saline groundwater infiltrates the buffer material. Therefore, the selection of the hydraulic parameters of the buffer material greatly affects the simulation results of the re saturation behaviour of the buffer material. In the Horonobe EBS experiment, measured values suitable for validating the simulation results were not obtained near the simulated overpack. When simulating the pressure and deformation of the buffer material, the measurement data is easily affected by the installation conditions of the measurement sensors, so verifying the measurement data itself remains an issue. Mechanical simulation results differ depending on whether they are considered as elastic or elastoplastic phenomena. The accuracy of measured in-situ data can be assessed by detailed analysis comparing sampling specimen analysis and measured data. The Horonobe EBS experiment is scheduled to be dismantled in the future (FY2026 and 2027). This detailed dismantling investigation will finally confirm the measured data.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2022

The System for on-Axis Neutrino Detection at the DUNE Near Detector complex

The Deep Underground Neutrino Experiment Near Detector complex aims at constraining the systematic uncertainties and deconvolving the neutrino beam flux and cross-section models. The System for on-Axis Neutrino Detection (SAND) is the Near Detector component permanently on-axis. SAND is based on the 0.6 T superconducting magnet and electromagnetic calorimeter previously used in the KLOE experiment. The 40 m3 magnetic volume will be filled with an active target/tracker system. One considered option foresees an upstream liquid Argon active target (about 1.5 t) and a Straw Tube Tracker (about 5 t). In this talk the design of SAND will be described and its performances discussed in view of the SAND primary goals, namely the beam monitoring and neutrino flux measurements.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

NASA NTRS1978

Decomposition of N2O over particulate matter

Nitrous oxide is shown to undergo both a thermal and a photochemical decomposition at 296 K when it is adsorbed on various dry sands. The photochemical process occurs with light of wavelengths greater than 280 nm, where gaseous N2O does not absorb. At low pressures (less than 0.1 torr) the half-life for the thermal decomposition of nitrous oxide to nitrogen when placed in contact with about 5 gm of heat-treated Tunisian sand in a one-liter vessel was 350 + or - 35 days. Under certain photolytic conditions this half-life was reduced. The efficiency of the photolytic process for a particular sand depends on the pressure and on the wavelength of light. For Tunisian sand at 1.1 torr and with the full mercury arc, the destruction efficiency is about 0.00002 molecule/incident photon. These results indicate that particulate matter in the troposphere may be responsible for the decomposition of nitrous oxide and hence act as an atmospheric sink for N2O. However, moisture causes a drastic reduction in the number of molecules dissociated per incident photon.

Rebbert, R. E.↗