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At least 973 records · Page 54

In Situ X-ray Absorption Spectroscopy Studies of Nanoscale Electrocatalysts

Nanoscale electrocatalysts have exhibited promising activity and stability, improving the kinetics of numerous electrochemical reactions in renewable energy systems such as electrolyzers, fuel cells, and metal-air batteries. Due to the size effect, nano particles with extreme small size have high surface areas, complicated morphology, and various surface terminations, which make them different from their bulk phases and often undergo restructuring during the reactions. These restructured materials are hard to probe by conventional ex-situ characterizations, thus leaving the true reaction centers and/or active sites difficult to determine. Nowadays, in situ techniques, particularly X-ray absorption spectroscopy (XAS), have become an important tool to obtain oxidation states, electronic structure, and local bonding environments, which are critical to investigate the electrocatalysts under real reaction conditions. In this review, we go over the basic principles of XAS and highlight recent applications of in situ XAS in studies of nanoscale electrocatalysts.

42 ENGINEERING↗

Boosting CO 2 reduction on Fe-N-C with sulfur incorporation: Synergistic electronic and structural engineering

Developing earth-abundant efficient catalysts for CO 2 reduction reaction (CO 2 RR) is of paramount importance for electrochemical conversion of CO 2 into value-added products. Despite numerous studies on iron and nitrogen codoped carbon (Fe-N-C) catalysts, grand challenges exist due to limited performance and understanding of catalytic mechanisms. This study reports a general strategy to boost electrocatalytic CO 2 RR activity of Fe-N-C with the incorporation of S atoms to engineer carbon support structure and electronic properties of active Fe-N sites simultaneously via a copolymer-assisted synthetic approach. The employment of N,S comonomers significantly increases the numbers of micropores and surface area, enabling dense atomic Fe-N and enhanced utilization efficiency. We report the first-principles calculations reveal that S modulation upraises the Fermi energy of Fe 3d and increases charge density on Fe atoms of Fe-N 4 , thereby enhancing intrinsic catalytic reactivity and selectivity for CO 2 reduction by strengthening the binding interaction between the Fe site and key COOH* intermediate. These integrated structural and electronic merits endow Fe-NS-C with outstanding activity (e.g., CO Faradaic efficiency of 98% at an overpotential of 490 mV) and stability (without deactivation in 30 h), ranking it one of the most active Fe-N-C reported to date. The finding offers an innovative design strategy to enable the design of advanced catalysts for CO 2 conversion.

25 ENERGY STORAGE↗

Per- and Polyfluoroalkyl Substances Confirmatory Sampling Report, South Repeater Building (SWMU 121), Kennedy Space Center, Florida

This Per- and Polyfluoroalkyl Substances (PFAS) Confirmatory Sampling (CS) Report was prepared by AECOM Technical Services, Inc. (AECOM) for the National Aeronautics and Space Administration (NASA) under Contract 80KSC019D0010, Task Order 80KSC021F0096. The purpose of this report is to document CS activities at the South Repeater Building, Solid Waste Management Unit (SWMU) 121, formerly known as the Area 3 Repeater Building (A3RB). A Phase I SWMU Assessment and Confirmatory Sampling Report (NASA 2019) and a Phase II and III SWMU Assessment and Confirmatory Sampling Report (NASA 2022b) were previously submitted detailing Center-Wide assessment activities performed at the John F. Kennedy Space Center (KSC) in Florida that identified 33 locations of concern and 19 areas of potential concern at KSC associated with the storage, use, or release of materials containing PFAS. A review of the analytical results from investigation derived waste samples collected in 2020 from the South Repeater Building area indicated concentrations of perfluorooctanesulfonic acid (PFOS) were above Florida Department of Environmental Protection (FDEP) provisional Groundwater Cleanup Target Levels of 70 nanograms per liter (ng/L) at a concentration of 1,750 ng/L. Following this review, the KSC Fire Chief was contacted; the Chief recalled fighting a brush fire in 1998 in the area, during which an unknown volume of aqueous film-forming foam was used to extinguish the fire. The Phase II and Phase III SWMU Assessment Report recommended this area proceed to CS. Historical results in this area are provided in Appendix A . PFAS CS activities were contracted at the South Repeater Building. Initial CS activities were conducted in accordance with the PFAS Assessment and Mitigation Work Plan (AECOM 2022), which was submitted to the NASA Remediation Project Management team and accepted by the team on November 1 and 8, 2021. The objectives of the PFAS CS were to: - - Confirm and begin to assess the extent of PFAS affected media in the South Repeater Building area. - - Identify locations for groundwater, soil, surface water, and soil core sampling. - - Qualitatively characterize the migration potential of released PFAS to environmental media (soil, groundwater, and surface water). The following activities were completed to meet the PFAS CS objectives: - - Installation of monitoring wells via direct push technology (DPT) and rotosonic techniques - - Groundwater, soil, and surface water sampling - - Collection of soil cores to evaluate site lithology - - Development of initial PFAS plume characterization

PFAS↗

Enhanced CO 2 Methanation Activity of Sm 0.25 Ce 0.75 O 2-δ –Ni by Modulating the Chelating Agents-to-Metal Cation Ratio and Tuning Metal–Support Interactions

Highly active and selective CO 2 methanation catalysts are critical to CO 2 upgrading, synthetic natural gas production, and CO 2 emission reduction. Wet impregnation is widely used to synthesize oxide-supported metallic nanoparticles as the catalyst for CO 2 methanation. However, as the reagents cannot be homogeneously mixed at an atomic level, it is challenging to modulate the microstructure, crystal structure, chemical composition, and electronic structure of catalysts via wet impregnation. In this work, a scalable and straightforward catalyst fabrication approach has been designed and validated to produce Sm 0.25 Ce 0.75 O 2-δ -supported Ni (SDC–Ni) as the CO 2 methanation catalyst. By varying the chelating agents-to-total metal cations ratio (C/I ratio) during the catalyst synthesis, we can readily and simultaneously modulate the microstructure, metallic surface area, crystal structure, chemical composition, and electronic structure of SDC–Ni, consequently fine-tuning the oxide–support interactions and CO 2 methanation activity. The optimal C/I ratio (0.1) leads to an SDC–Ni catalyst that facilitates C–O bond cleavage and significantly improves CO 2 conversion at 250 °C. A CO 2 -to-CH 4 yield of >73% has been achieved at 250 °C. Furthermore, a stable operation of >1500 hours has been demonstrated, and no degradation is observed. Extensive characterizations were performed to fundamentally understand how to tune and enhance CO 2 methanation activity of SDC–Ni by modulating the C/I ratio. The correlation of physical, chemical, and catalytic properties of SDC–Ni with the C/I ratio is established and thoroughly elaborated in this work. This study could be applied to tune the oxide–support interactions of various catalysts for enhancing the catalytic activity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Near Space Tracking of the EM Phenomena Associated with the Main Earthquakes

Searching for electromagnetic (EM) phenomena originating in the Earth's crust prior to major earthquakes (M>5) are the object of this exploratory study. We present the idea of a possible relationship between: (1) electro-chemical and thermodynamic processes in the Earth's crust and (2) ionic enhancement of the atmosphere/ionosphere with tectonic stress and earthquake activity. The major source of these signals are proposed to originate from electromagnetic phenomenon which are responsible for these observed pre-seismic processes, such as, enhanced IR emission, also born as thermal anomalies, generation of long wave radiation, light emission caused by ground-to-air electric discharges, Total Electron Content (TEC) ionospheric anomalies and ionospheric plasma variations. The source of these data will include: (i) ionospheric plasma perturbations data from the recently launched DEMETER mission and currently available TEC/GPS network data; (ii) geomagnetic data from ORSTED and CHAMP; (iii) Thermal infra-red (TIR) transients mapped by the polar orbiting (NOAA/AVHRR, MODIS) and (iv) geosynchronous weather satellites measurements of GOES, METEOSAT. This approach requires continues observations and data collecting, in addition to both ground and space based monitoring over selected regions in order to investigate the various techniques for recording possible anomalies. During the space campaign emphasis will be on IR emission, obtained from TIR (thermal infrared) satellites, that records land/sea surface temperature anomalies and changes in the plasma and total electron content (TEC) of the ionosphere that occur over areas of potential earthquake activity.

Ouzounov, Dimitar↗

Gd-cobalt selenite as an efficient nanocomposite for aniline synthesis from photocatalytic reduction of nitrobenzene

Highlights: • Gd-CoSeO{sub 3} nanocomposites were prepared via Sol- Gel method. • The effect of weight percent of Gd on the morphology of products were investigated. • 0.3 wt% Gd-CoSeO{sub 3} exhibited the highest catalytic activity for reduction of nitrobenzene under visible light. - Abstract: In this investigation, Gd-CoSeO{sub 3} nanocomposite with controlled Gd doping contents was synthesized using a sol gel method. The resultant specimen was found to have large specific surface area (115 m{sup 2}/g) and limited particle size (15 nm). TEM examination illustrated that the synthesized Gd-CoSeO{sub 3} nanocomposite exhibited nanospherical morphology. Also, it was revealed that band gap controlling of the CoSeO{sub 3} nanoparticles could be accomplished via managing the Gd contents. The photocatalytic activity of the Gd-CoSeO{sub 3} nanocomposite samples was inspected via Nitrobenzene – aniline transformation applying visible light irradiation. Gadolinium doping was adopted to improve the photo-catalytic of the synthesized CoSeO{sub 3}. This can be accredited to band gap decrease of CoSeO{sub 3} by Gd doping as well as life time increase of e-h recombination rate which occur via electron trapping by Gd metal. Therefore, we can prepare an efficient photocatalyst by sol- gel method and photoassisted deposition method to control band gap and e-h recombination rate.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Findings on Subtask 3.1 - Bakken Rich Gas Enhanced Oil Recovery Project

Total in-place oil for the Bakken petroleum system (BPS) (which includes the Bakken and Three Forks Formations) has been estimated to be 600 billion barrels (bbl). However, BPS wells have decline rates as high as 85% over the first 3 years of their lives, and primary recovery factors typically range from 3% to 10% of original oil in place. Given the low initial recovery rates, even small incremental productivity improvements could dramatically increase technically recoverable oil in the BPS. One potential solution is enhanced oil recovery (EOR) using gas injection, such as carbon dioxide (CO2) or hydrocarbon (HC) gases. While commonly used in conventional reservoirs, CO2 EOR in unconventional tight oil reservoirs has been limited to pilot tests. EOR using rich gas (mixture of methane, ethane, and propane) has also been employed in numerous pilots in several unconventional plays and has recently been successfully applied in the Eagle Ford play. If successful, large-scale gas-based EOR in the BPS could dramatically increase oil productivity and recovery factors and extend the life of the play for decades. While CO2 may be a technically suitable working fluid for EOR in the BPS, supplies are limited and costs for using CO2 in EOR pilots are prohibitively high. Meanwhile, produced gas flaring has presented challenges for BPS operators in North Dakota. Analysis conducted by the North Dakota Pipeline Authority indicates that the current gas-gathering infrastructure in North Dakota is insufficient to accommodate all of the associated gas that is produced from the BPS. The geographically isolated location of North Dakota relative to large natural gas markets, combined with suppressed natural gas prices, has made it economically challenging for industry to invest capital in expanding gas-gathering infrastructure in the state. These circumstances led to a research program conducted by the Energy & Environmental Research Center (EERC) in partnership with Liberty Resources Management Company LLC (LR) to examine the potential to use rich gas injection for EOR and mitigate flaring. A rich gas EOR pilot test was designed and executed by LR at its Stomping Horse development area in Williams County, North Dakota. From July 2018 through May 2019, a total of 160 million standard cubic feet (MMscf) of rich produced gas was injected into the BPS using five different wells in a sequential injection strategy. LR’s Leon–Gohrick drill spacing unit (DSU) was used as the test site. Regulatory oversight was provided by the North Dakota Industrial Commission (NDIC). Technical support was provided by the EERC through a series of laboratory, modeling, and field-based activities, and additional post-pilot research activities incorporated learnings from the test, developed new laboratory data, improved fracture modeling methods, and developed machine learning and big data analytics. The results from the Stomping Horse rich gas EOR pilot activities indicate that developing an effective, economical EOR approach for the BPS will require more field tests. Another key lesson learned from the Stomping Horse tests is that detailed pre- and posttest data on reservoir conditions and fluids production are essential. Robust reservoir characterization provides information that is crucial to creating realistic geomodels and conducting valid dynamic simulations of potential EOR scenarios. A detailed understanding of the completions and production history of offset wells is also necessary for valid test result interpretations. This knowledge is essential to designing the operational parameters of injectivity tests and interpreting the results. A conformance control strategy is also essential to success. Laboratory-based examinations of rich gas interactions with reservoir fluids and rocks were conducted, with an emphasis on determining the ability to mobilize oil in the tight reservoir rocks and shales of the BPS. Injection fluid composition was shown to have a positive impact on reducing reservoir oil minimum miscibility pressure (MMP), reducing interfacial tension (IFT), and altering wettability. IFT and contact angle measurements demonstrated that wettability can be altered in the presence of rich gas, suggesting the potential to improve oil recovery. Iterative modeling of surface infrastructure and reservoir performance using data generated by the various project activities was conducted. A geologic model of the Stomping Horse area was built; history-matched oil, gas, and water production was used in simulations of various EOR scenarios. Early programmatic modeling results were used to support LR’s design and operation of the EOR pilot and to provide insight regarding optimization of future commercial-scale BPS EOR design and operations. Post-pilot modeling focused on alternative methods of understanding complex fracture networks and accelerating simulation time. These led to improved simulation run times and provide excellent history-matching results. Several of these iterative models were used as the bases for developing algorithms into machine learning and big data analytics. History matching in reservoir simulation is time-consuming and computer processing-intensive. Machine learning algorithms were created, and an automated history-matching tool was developed. A large set of synthetic reservoir simulations were created to generate well responses (oil, gas, and water production, well bottomhole pressure [BHP], and tracer or propane breakthrough) for a set of EOR operating parameters that included offset well status (open or closed), injectate (rich gas or propane), injection rate, and injection well BHP. A user interface was developed to provide real-time visualization. Machine learning-based models were developed to provide rapid forecasting of well performance given a set of user-defined EOR operating parameters. These predictive models allow the user to modify the offset well status, injection rate, and injection well BHP and rapidly forecast future production performance. The combination of real-time visualization tools with real-time forecasting tools provides a framework for real-time control—operational changes that the EOR site operator can enact (e.g., changing gas injection rates) to affect the observed performance and potentially improve the EOR outcome. There is great reason to be optimistic about the future of EOR in the Bakken. The results of the laboratory studies suggest significant potential for high rates of oil mobilization using produced field gas injection under the right conditions. The results of the lab studies, combined with rigorous statistical analysis of well production data and associated modeling efforts, confirm the notion that fluid mobility within the reservoir is controlled by fractures. As more knowledge is gained about the nature and distribution of fracture networks in the Bakken, the industry will be in a better position to predict and, ultimately, influence fluid mobility. New field tests are necessary to develop a more complete understanding of those conditions. Thoughtful and creatively engineered field tests within a well-characterized geologic setting will yield the fundamental knowledge needed to take Bakken oil production to the next level. This subtask was cofunded through the EERC–U.S. Department of Energy Joint Program on Research and Development for Fossil Energy-Related Resources Cooperative Agreement No. DE-FE0024233. Nonfederal funding was provided by the North Dakota Industrial Commission’s Oil and Gas Research Program and Computer Modelling Group.

04 OIL SHALES AND TAR SANDS↗

Enhanced catalytic activity of mesoporous graphitic carbon nitride on thermal decomposition of ammonium perchlorate via copper oxide modification

Highlights: • Novel mpg-C{sub 3}N{sub 4}/rod-like CuO nanocomposites were synthesized via a facile precipitation method for the first time. • The BET surface area of as-synthesized mpg-C{sub 3}N{sub 4}/CuO is 111.33 m{sup 2} g{sup −1}, which is beneficial for catalyzing the thermal decomposition process of ammonium perchlorate (AP). • The synergistic effect between mpg-C{sub 3}N{sub 4} and CuO was the origin of the high catalytic activity. • The mpg-C{sub 3}N{sub 4}/CuO nanocomposites were applied in catalyzing the thermal decomposition of AP and the proposed catalytic mechanism was also proposed. - Abstract: Aiming at enhancing the catalytic activity of mpg-C{sub 3}N{sub 4} on thermal decomposition of ammonium perchlorate, mpg-C{sub 3}N{sub 4} was successfully modified by CuO nanorods, via a facile precipitation method. The structure, morphology and composition of mpg-C{sub 3}N{sub 4} and mpg-C{sub 3}N{sub 4}/CuO nanocomposites were characterized by nitrogen adsorption-desorption measurements, transmission electron microscopy, scanning electron microscope, X-ray power diffraction, fourier transform infrared spectroscopy, as well as X-ray photoelectron spectroscopy. The results demonstrated that CuO nanorods (length of 200–300 nm, diameter of 10–15 nm) were uniformly dispersed throughout mpg-C{sub 3}N{sub 4}, efficiently avoiding the agglomeration. Finally, it was demonstrated that the high weight-loss decomposition temperature of AP was decreased up to 118.5 °C in the presence of 2 wt% mpg-C{sub 3}N{sub 4}/CuO nanocomposites, which was higher than that of pure mpg-C{sub 3}N{sub 4} and CuO, respectively, demonstrating the catalytic performances of the nanocomposites was enhanced via the synergistic catalysis between mpg-C{sub 3}N{sub 4} and CuO.

36 MATERIALS SCIENCE↗

Syntheses of ZnO with Different Morphologies: Catalytic Activity toward Coumarin Synthesis via the Knoevenagel Condensation Reaction

Heterogeneous catalysts are preferred in fine chemical industries due to their easy recovery and reusability. In this work, we report an easily scalable method of ZnO catalysts for coumarin synthesis. Nanocrystalline ZnO particles with diverse morphologies and crystallite sizes were prepared using different solvents. The change in morphology results in changes in band gaps, defects, basicity, and textural properties (surface areas, pore volumes, and pore sizes). The catalytic performances of the synthesized ZnO materials were tested using coumarin synthesis via the Knoevenagel condensation. The catalyst synthesized using methanol shows the highest activity and selectivity (conversion of 74%, selectivity of 94%) with a turnover number of 14.69. The increased activity of the ZnO synthesized in methanol is attributed to the combined effects of moderate basicity and relatively high textural properties of the sample.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

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↗

Ligand removal of Au 25 nanoclusters by thermal and electrochemical treatments for selective CO 2 electroreduction to CO

Undercoordinated metal nanoclusters have shown great promise for various catalytic applications. However, their activity is often limited by the covalently bonded ligands, which could block the active surface sites. Here, we investigate the ligand removal process for Au 25 nanoclusters using both thermal and electrochemical treatments, as well as its impact on the electroreduction of CO 2 to CO. The Au 25 nanoclusters are synthesized with 2-phenylethanethiol as the capping agent and anchored on sulfur-doped graphene. The thiolate ligands can be readily removed under either thermal annealing at ≥180°C or electrochemical biasing at ≤-0.5 V vs reversible hydrogen electrode, as evidenced by the Cu underpotential deposition surface area measurement, x-ray photoelectron spectroscopy, and extended x-ray absorption fine structure spectroscopy. However, these ligand-removing treatments also trigger the structural evolution of Au 25 nanoclusters concomitantly. The thermally and electrochemically treated Au 25 nanoclusters show enhanced activity and selectivity for the electrochemical CO 2 -to-CO conversion than their pristine counterpart, which is attributed to the exposure of undercoordinated Au sites on the surface after ligand removal. This work provides facile strategies to strip away the staple ligands from metal nanoclusters and highlights its importance in promoting the catalytic performances.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A consideration of radionuclide particulate resuspension as a verification tool in the CTBT on-site inspection verification component

Here, a considerable amount of radioactivity could leak from an underground nuclear test at levels easily detectable by one or more of the radiological methods available for on-site inspection, even if the event does not immediately result in gas or particulate debris reaching stations of the International Monitoring System, of the Comprehensive Nuclear-Test-Ban Treaty. This work presents a feasibility study showing that winds or human activity can resuspend surface debris in quantities that could be detected using high-volume aerosol samplers outside an established restricted area and subsequent measurement in a Base of Operations laboratory.

CTBT↗

Using Dark Fiber and Distributed Acoustic Sensing to Characterize a Geothermal System in the Imperial Valley, Southern California

The Imperial Valley, CA, is a tectonically active transtensional basin located south of the Salton Sea; the area hosts numerous geothermal fields, including significant hidden hydrothermal resources without surface manifestations. Development of inexpensive, rugged, and highly sensitive exploration techniques for undiscovered geothermal systems is critical for accelerating geothermal power deployment as well as unlocking a low-carbon energy future. We present a case study utilizing distributed acoustic sensing (DAS) and ambient noise interferometry for geothermal reservoir imaging, utilizing unlit fiber-optic telecommunication infrastructure (dark fiber). The study exploits two days of passive DAS data acquired in early November 2020 over a ~28-km section of fiber from Calipatria, CA to Imperial, CA. We apply ambient noise interferometry to retrieve coherent signals from DAS records and develop a bin stacking technique to attenuate the effects from persistent localized noise sources and to enhance retrieval of coherent surface waves. As a result, we are able to obtain high-resolution two-dimensional (2D) S wave velocity ($V_s$) structure to 3 km depth, based on joint inversion of both the fundamental and higher overtones. We observe a previously unmapped high $V_s$ and low $V_p$/$V_s$ ratio feature beneath the Brawley geothermal system, which we interpret to be a zone of hydrothermal mineralization and lower porosity. This interpretation is consistent with a host of other measurements including surface heat flow, gravity anomalies, and available borehole wireline data. These results demonstrate the potential utility of DAS deployed on dark fiber for geothermal system exploration and characterization in the appropriate geological settings.

Vp/Vs imaging↗

Machine-learning-assisted material discovery of oxygen-rich highly porous carbon active materials for aqueous supercapacitors

Abstract Porous carbons are the active materials of choice for supercapacitor applications because of their power capability, long-term cycle stability, and wide operating temperatures. However, the development of carbon active materials with improved physicochemical and electrochemical properties is generally carried out via time-consuming and cost-ineffective experimental processes. In this regard, machine-learning technology provides a data-driven approach to examine previously reported research works to find the critical features for developing ideal carbon materials for supercapacitors. Here, we report the design of a machine-learning-derived activation strategy that uses sodium amide and cross-linked polymer precursors to synthesize highly porous carbons (i.e., with specific surface areas > 4000 m 2 /g). Tuning the pore size and oxygen content of the carbonaceous materials, we report a highly porous carbon-base electrode with 0.7 mg/cm 2 of electrode mass loading that exhibits a high specific capacitance of 610 F/g in 1 M H 2 SO 4 . This result approaches the specific capacitance of a porous carbon electrode predicted by the machine learning approach. We also investigate the charge storage mechanism and electrolyte transport properties via step potential electrochemical spectroscopy and quasielastic neutron scattering measurements.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Highly uniform distribution of Pt nanoparticles on N-doped hollow carbon spheres with enhanced durability for oxygen reduction reaction

Here, carbon-supported Pt nanostructures currently exhibited great potential in polymer electrolyte membrane fuel cells. Nitrogen-doped hollow carbon spheres (NHCSs) with extra low density and high specific surface area are promising carbon support for loading Pt NPs. The doped heteroatom of nitrogen could not only contribute to the active activity for the oxygen reduction reaction (ORR), but also shows a strong interaction with Pt NPs for entrapping them from dissolution/migration. This synergetic effect/interaction resulted in the uniform dispersion and strong combination of the Pt NPs on the carbon support and thus play a significant role in hindering the degradation of the catalytic activities of Pt NPs. As expected, the as-obtained Pt/NHCSs displayed improved catalytic activity and superior durability toward ORR.

36 MATERIALS SCIENCE↗

γ-Valerolactone-Extracted Lignin to Porous Carbon Materials

Synthesis of multiphase materials from lignin, a biorefinery coproduct, offers limited success due to the inherent difficulty in controlling dispersion of these renewable hyperbranched macromolecules in the product or its intermediates. Effective use of the chemically reactive functionalities in lignin, however, enables tuning morphologies of the materials. Here, we bind a lignin oligomer with a rubbery macromolecule followed by thermal crosslinking to form a carbon precursor with phase contrasted morphology at submicron scale. The solvent-free mixing is conducted in a high-shear melt-mixer. With this, the carbon precursor is further modified with potassium hydroxide for a single-step carbonization to yield activated carbon with tunable pore structure. A typical precursor with 90% lignin yields porous carbon with 2120 m 2 /g surface area and a supercapacitor with 215 F/g capacitance. The results show a simple route towards manufacturing carbon-based energy-storage materials, eliminating the need for conventional template-synthesis.

36 MATERIALS SCIENCE↗

Review of composite propellant burn rate modeling

Steady-state combustion modeling of composite solid propellants is discussed with emphasis on the Beckstead-Derr-Price (BDP) model. The BDP model and some revisions are considered with respect to the analysis of monomodal ammonium perchlorate/inert binder propellants: topics examined include continuity relations, surface area relations, characteristic surface dimension, flame heights, and energy balance. Application of the BDP model to more complicated propellants containing multiple active ingredients is described. These propellants include multimodal, mixed oxidizer, active binder, aluminized, catalyzed, and nitramine propellants. Example cases of modeling (with comparison to experimental data) are presented, and strengths and weaknesses of current modeling approaches are evaluated.

Cohen, N. S.↗

The evolution of the polar coronal holes

He I 10830 A synoptic maps, obtained at the Kitt Peak National Observatory during 1974-1979, show that the sun's polar coronal holes have contracted significantly during 1977-1978. Prior to the accelerated increase of sunspot activity in mid-1977, the area of each polar cap was on the order of 8% of the sun's total surface area, whereas toward the end of 1978 these areas fell below 2% of the total surface area. Synoptic polar plots show that the vestigial holes had irregular shapes and were often well removed from the poles themselves. These results are consistent with the changes that one would expect when the polar magnetic fields are weakening just prior to sunspot maximum

Sheeley, N. R., Jr.↗