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Sustainable Remediation of Radionuclides By a Common Sense Approach to Enhanced Attenuation - 16441

Development of in situ and relatively passive remedies for treatment of groundwater contaminated by metals and radionuclides is becoming more important because of the difficulty and cost - both to the environment and financially -- of removing these types of contaminants from the subsurface by pump-and-treat or excavation. In situ technologies rely on reactions that tend to remove contaminants from groundwater by partitioning them to solid phases in the aquifer. Monitored natural attenuation (MNA) relies solely on natural reactions to achieve remedial goals. Enhanced attenuation (EA) uses engineered approaches to supplement remediation when MNA is not sufficient to meet remedial goals. Both approaches leave contaminants in the subsurface and require a high burden of proof that contaminants will not be mobilized and become a risk in the future. Proof of the sustained effectiveness of an EA remedy is made much easier by strategic design. In multi-contaminant plumes, it is important to prioritize contaminants according to the risk they pose, with the recognition that one remedy rarely treats all contaminants. The goal for the engineered portion of the remedy should be maximum risk reduction with minimal engineering. Natural attenuation or negotiated alternate concentration levels will often allow low risk contaminants to go untreated. Whenever possible, the remedy should be consistent with the geochemical evolution of the waste site, insuring that the treated immobilized contaminants are likely to remain relatively immobile for long time frames. Finally, use what nature provides geologically, hydrologically, geochemically, or microbiologically in the remedy design. One of the impediments faced by waste site managers in implementing EA remedies is paralysis by perceived complexity. There are things that must be known to design an effective EA remedy, but there is always the temptation to know everything to eliminate the possibility of failure. Furthermore, there are plenty of people warning of failure if all is not known and they are usually willing to help the design team know all, for a price. Yet, the price of trying to eliminate all risk is never implementing an innovative remedy. All parties involved -- scientists/engineers, waste site managers, regulators and stakeholders must assume some degree of risk to deploy an EA remedy. If all parties are to assume some risk, then trust built through close communication from the start is required. The U.S. Department of Energy Office of Environmental Management has funded an applied field research initiative for several years focused, in part, on developing EA remedies for metals and radionuclides using these guiding principles. This approach to EA remedies grew out of developing and deploying a remediation strategy to replace a pump-and-treat system at the F-Area Seepage Basins on the Savannah River Site. The pump-and-treat system was energy intensive, produced several thousand cubic feet of solid radioactive waste per year, and cost $ 1 million per month to operate. The EA remedy that replaced the pump-and-treat is energy efficient, produces no waste, and costs approximately $1 million per year to maintain. At the F-Area Seepage Basins approximately 7 billion liters of low level radioactive waste solutions were disposed in three unlined basins resulting in contaminated groundwater containing various radionuclides and other contaminants. The primary contaminants of concern are tritium, strontium-90, uranium, and iodine-129. Other key features of the contaminant plume are its acidic nature with pH values as low as 3.2, its vertical stratification in the water table aquifer, and the tendency of the most contaminated portions to follow troughs in the top of the clay separating the upper aquifer zone from the lower aquifer zone. The geology was exploited by installing a funnel-and-gate system into the clay with the barrier portion blocking contaminant flow paths in the troughs in the clay. This forces the most contaminated water to flow through the gates where it encounters an in situ treatment zone created by periodic injections of alkaline solution. The flux of tritium has been reduced significantly by the barrier walls. Strontium-90 and uranium are treated by enhanced sorption in the circum-neutral pH treatment zone, consistent with natural geochemical evolution of the waste site from acidic to more neutral pH. An additional in situ treatment zone was created up-gradient of the one of the gates to treat iodine-129. Sub-micrometer diameter silver chloride particles were injected into the aquifer by direct push methods to create the treatment zone. In the laboratory and in a field pilot test the poorly soluble silver chloride particles reacted with iodide to form much less soluble silver iodide. Evaluation of the effectiveness of the silver chloride is ongoing. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Development of HPWH System Model, Using All Microchannel Heat Exchangers

In this report, 24-hour energy factor (EF) and first-hour draw rating (FHR) simulations were conducted on two heat pump water heater systems (HPWHs), one using a fin-and-tube evaporator and wrapped-tank condenser coil with D-shape tubes, and the other using a micro-channel evaporator and wrapped-tank condenser coil with microchannel tubes. Alternative refrigerants as drop-in replacements of R-134a were evaluated, including R-1234yf, R-1234ze(E), propane (R-290), R-450A and R-513A. The results are summarized below: 1.Microchannel heat exchangers can decrease the system charge down to 30% relative to fin-and-tube evaporator and wrapped-tank D tubes.2.Having the same contact surface area to the water tank and evaporator frontal flow area, the system using microchannel heat exchangers (MHXs) results in 5% efficiency degradation. Due to the very small cross-sectional flow area of a microchannel tube, MHXs tend to have multiple parallel tubes to restrict the refrigerant pressure drop. The parallel pattern can’t utilize the water temperature stratification as effectively as the D-shape tubes, which are arranged in one or two circuits and counter flow to the water stratification. 3.Refrigerant drop-in system simulations were conducted for R-1234yf, R-1234ze(E), propane, R450A and R513A in comparison to R-134a. Among the alternatives, propane has the largest volumetric capacity, which results in shortest HPWH run time and highest first-hour rating. Propane leads to the smallest energy factor because its largest volumetric capacity overloads the heat exchangers. R-1234ze(E) has the smallest volumetric capacity, highest energy factor, but smallest first-hour rating. R-1234yf, R-450A and R-513A achieve similar performance indices as R-134a. 4.Propane requires the least refrigerant mass (45% relative to R-134a). If a wrapped-tank microchannel condenser and microchannel evaporator are used, the required system charge can be limited below 150 grams, which makes it feasible to use propane for domestic HPWH.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

On the Representation of the Porosity-Pressure Relationship in General Subsurface Flow Codes

The governing equations for subsurface flow codes in a deformable porous media are derived from the balance of fluid mass and Darcy's equation. One class of these codes, which we call general subsurface flow codes (GSFs), allow for more general constitutive relations for material properties such as porosity, permeability and density. Examples of GSFs include PFLOTRAN, FEHM, TOUGH2, STOMP, and some reservoir simulators such as BOAST. Depending on the constitutive relations used in GSFs, an inconsistency arises between the standard groundwater flow equation and the governing equation of GSFs, and we clarify that the reason for this inconsistency is because the Darcy's equation used in the GSFs should account for the velocity of fluid with respect to solid. Due to lack of awareness of this inconsistency, users of the GSFs tend to use a porosity-pressure relationship that comes from the standard groundwater flow equation and assumes that the relative velocity is already accounted for. For the Theis problem, we show that using this traditional relationship in the GSFs leads to significantly large errors. In this work, we propose an alternate porosity-pressure relationship that is consistent with the derivation of the governing equations in the GSFs where the solid velocity is not tracked, and show that, with this relationship, the results are more accurate for the Theis problem. The purpose of this note is to make the users and developers of these GSFs aware of this inconsistency and to advocate that the alternate porosity model derived here should be incorporated in GSFs.

58 GEOSCIENCES↗

An analytic result for the 0 → ggHHH amplitude

We present a fully analytic calculation of the leading-order one-loop amplitude for triple Higgs production via gluon fusion, gg → HHH, retaining full dependence on the mass of the heavy quark circulating in the loop. This amplitude provides a direct probe of the triple and quartic Higgs self-couplings, the measurement of which is a central goal of current and future colliders. The amplitude can be presented in compact form thanks to the use of analytic reconstruction techniques, based on finite-field and p-adic evaluations, multivariate partial fraction decompositions, and primary decompositions to identify common numerator factors. Although full analytic results are given in the text and in the supplementary material, the main thrust of this paper is to further test and illustrate these analytic reconstruction techniques in a concrete physical example. Our results provide a compact and efficient representation of the matrix element for this process, enabling evaluations that are more than an order of magnitude faster than existing numerical alternatives. Full analytic control of the leading-order, loop-induced amplitude is an important step towards handling more complex 2-loop or real-radiation corrections to this and related processes.

Campbell, John M. [Fermilab] (ORCID:00000002136193↗

Ambient aging of rhenium filaments used in thermal ionization mass spectrometry: Growth of oxo-rhenium crystallites and anti-aging strategies

Degassing is a common preparation technique for rhenium filaments used for thermal ionization mass spectrometric analysis of actinides, including plutonium. Although optimization studies regarding degassing conditions have been reported, little work has been done to characterize filament aging after degassing. In this study, the effects of filament aging after degassing were explored to determine a “shelf-life” for degassed rhenium filaments, and methods to limit filament aging were investigated. Zone-refined rhenium filaments were degassed by resistance heating under high vacuum before exposure to ambient atmosphere for up to 2 months. After degassing the nucleation and preferential growth of oxo-rhenium crystallites on the surface of polycrystalline rhenium filaments was observed by atomic force microscopy and scanning electron microscopy (SEM). Compositional analysis of the crystallites was conducted using SEM-Raman spectroscopy and SEM energy dispersive X-ray spectroscopy, and grain orientation at the metal surface was investigated by electron back-scatter diffraction mapping. Spectra collected by SEM-Raman suggest crystallites are composed primarily of perrhenic acid. The relative extent of growth and crystallite morphology were found to be grain dependent and affected by the dissolution of carbon into filaments during annealing (often referred to as carbonization or carburization). Crystallites were observed to nucleate in region specific modes and grow over time through transfer of material from the surface. Factors most likely to affect the rates of crystallite growth include rhenium substrate properties such as grain size, orientation, levels of dissolved carbon, and relative abundance of defect sites; as well as environmental factors such as length of exposure to oxygen and relative humidity. Thin (~180 nm) hydrophobic films of poly(vinylbenzyl chloride) were found to slow the growth of oxo-rhenium crystallites on the filament surfaces and may serve as an alternative carbon source for filament carburization.

36 MATERIALS SCIENCE↗

Hole-Transport Layer for High Current Density and Stability of Sn-Pb Perovskites and All-Perovskite Tandem Solar Cells

Sn-Pb perovskites are essential for achieving efficient single-junction solar cells and all-perovskite tandem solar cells (APTSCs). Although Sn oxidation and defective surfaces were once major limitations, recent advances in intrinsic material quality have largely mitigated these issues. As a result, the HTL-related interface is now regarded as the primary bottleneck for device performance. To address the intrinsic drawbacks of PEDOT:PSS, chemical surface modification and additive strategies have been widely applied, and alternative HTLs, like polymeric, inorganic, or small-molecule HTLs, have also gained attention. These approaches offer improved energy-level alignment, high transparency, and enhanced chemical durability, leading to higher short-circuit current density and longer operational lifetime in both single-junction and tandem devices. In this Perspective, we highlight the key criteria and practical effects of HTL materials suitable for Sn-Pb perovskites.

14 SOLAR ENERGY↗

Polymer Architecture-Induced Trade-off between Conductivities and Transference Numbers in Salt-Doped Polymeric Ionic Liquids

Recent experiments have demonstrated that polymeric ionic liquids that share the same cation and anion but possess different architectures can exhibit markedly different conductivity and transference number characteristics when doped with lithium salt. In this study, we used atomistic molecular simulations on polymer chemistries inspired by the experiments to probe the mechanistic origins underlying the competition between conductivity and transference numbers. Our results indicate that the architecture of the polycationic ionic liquid plays a subtle but crucial role in modulating the anion–cation interactions, especially their dynamical coordination characteristics. Chemistries leading to longer-lived anion–cation coordinations relative to lithium–anion coordinations lead to lower conductivities and higher transference numbers. Furthermore, our results suggest that higher conductivities are accompanied by lower transference numbers and vice versa, revealing that alternative approaches may need to be considered to break this trade-off in salt-doped polyILs.

33 ADVANCED PROPULSION SYSTEMS↗

A GIS COST MODEL TO ASSESS THE AVAILABILITY OF FRESHWATER, SEAWATER, AND SALINE GROUNDWATER FOR ALGAL BIOFUEL PRODUCTION IN THE UNITED STATES

A key advantage of using microalgae for biofuel production is the ability of some algal strains to thrive in waters unsuitable for conventional crop irrigation such as saline groundwater or seawater. Nonetheless, the availability of sustainable water supplies will provide significant challenges for scale-up and development of algal biofuels. We conduct a limited techno-economic assessment based on the availability of freshwater, saline groundwater, and seawater for use in open pond algae cultivation systems. We explore water issues through GIS-based models of algae biofuel production, freshwater supply, and cost models for supplying seawater and saline groundwater. We estimate that combined, within the coterminous US these resources can support production on the order of 9.46E+7 m3 yr-1 (25 billion gallons yr-1) of renewable biodiesel. Achievement of larger targets requires the utilization of less water efficient sites and relatively expensive saline waters. Geographically, water availability is most favorable for the coast of the Gulf of Mexico and Florida peninsula, where evaporation relative to precipitation is moderate and various saline waters are economically available. As a whole, barren and scrub lands of the southwestern US have limited freshwater supplies so accurate assessment of alternative waters is critical.

biofuel↗

Mimicking Extradiol Dioxygenase Reactivity on Iridium

Extradiol dioxygenases catalyze the cleavage of benzenediol (catechol) or vicinal aminophenols via oxygen atom insertion into the 2,3- C–C bond. These reactions are most often proposed to proceed through the migratory rearrangement of a d6 alkylperoxide, generating the corresponding d 6 ring expanded product. However, regiospecific insertion remains a rare outcome among synthetic model complexes. Here, a dioxygenated Ir complex (2) converts to (a) the paramagnetic metallatrioxolane (3) and (b) oxygen atom inserted products (4) and (5); all three complexes are third-row metal analogues of enzymatic intermediates. The conversion of 2 to 3 was triggered by an H• abstraction, generating a third-row metallatrioxolane that is one electron reduced from the canonical d 6 alkylperoxide. Alternatively, photolysis of 2 (467 nm) results in ring-expanded product 4, from which an H• can be abstracted to generate 5. This latter complex is also one electron reduced relative to the canonical ring expansion product. Because extradiol mechanisms were largely defined using Fe(II) metallocofactors, 3 and 5 may be especially relevant to the known Co(II) accepting variants. We propose these states became synthetically accessible via the incorporation of a catechol-like substrate into the larger, multidentate ligand L1. This perturbation enhances the affinity of L1 (and related intermediates) to the metal. The same perturbation may have also been key in characterizing the first κ 2 -bound, dianionic ortho ester ligand – the observed binding mode in the x-ray structure of 5. Broadly, we propose through this case study that connecting abiological dioxygen complexes to non-heme oxygenase-like intermediates might be a “roadmap” towards regiospecific aerobic oxygenations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Preserving isohydricity: vertical environmental variability explains Amazon forest water-use strategies

Abstract Increases in hydrological extremes, including drought, are expected for Amazon forests. A fundamental challenge for predicting forest responses lies in identifying ecological strategies which underlie such responses. Characterization of species-specific hydraulic strategies for regulating water-use, thought to be arrayed along an ‘isohydric–anisohydric’ spectrum, is a widely used approach. However, recent studies have questioned the usefulness of this classification scheme, because its metrics are strongly influenced by environments, and hence can lead to divergent classifications even within the same species. Here, we propose an alternative approach positing that individual hydraulic regulation strategies emerge from the interaction of environments with traits. Specifically, we hypothesize that the vertical forest profile represents a key gradient in drought-related environments (atmospheric vapor pressure deficit, soil water availability) that drives divergent tree water-use strategies for coordinated regulation of stomatal conductance (gs) and leaf water potentials (ΨL) with tree rooting depth, a proxy for water availability. Testing this hypothesis in a seasonal eastern Amazon forest in Brazil, we found that hydraulic strategies indeed depend on height-associated environments. Upper canopy trees, experiencing high vapor pressure deficit (VPD), but stable soil water access through deep rooting, exhibited isohydric strategies, defined by little seasonal change in the diurnal pattern of gs and steady seasonal minimum ΨL. In contrast, understory trees, exposed to less variable VPD but highly variable soil water availability, exhibited anisohydric strategies, with fluctuations in diurnal gs that increased in the dry season along with increasing variation in ΨL. Our finding that canopy height structures the coordination between drought-related environmental stressors and hydraulic traits provides a basis for preserving the applicability of the isohydric-to-anisohydric spectrum, which we show here may consistently emerge from environmental context. Our work highlights the importance of understanding how environmental heterogeneity structures forest responses to climate change, providing a mechanistic basis for improving models of tropical ecosystems.

Forestry↗

Low-Cost Bio-Based Carbon Fibers for High Temperature Processing

GrafTech International Holdings Inc. (GTI), under Award No. DE-EE0005779, worked with Oak Ridge National Laboratory (ORNL) under CRADA No. NFE-15-05807 to develop lignin-based carbon fiber (LBCF) technology and to demonstrate LBCF performance in high-temperature products and applications. This work was unique and different from other reported LBCF work in that this study was application-focused and scalability-focused. Accordingly, the executed work was based on meeting criteria based on technology development, cost, and application suitability. High-temperature carbon fiber based insulation is used in energy intensive industries, such as metal heat treating and ceramic and semiconductor material production. Insulation plays a critical role in achieving high thermal and process efficiency, which is directly related to energy usage, cost, and product competitiveness. Current high temperature insulation is made with petroleum based carbon fibers, and one goal of this protect was to develop and demonstrate an alternative lignin (biomass) based carbon fiber that would achieve lower cost, CO2 emissions, and energy consumption and result in insulation that met or exceeded the thermal efficiency of current commercial insulation. In addition, other products were targeted to be evaluated with LBCF. As the project was designed to proceed in stages, the initial focus of this work was to demonstrate lab-scale LBCF from at least 4 different lignin precursor feedstock sources that could meet the estimated production cost of $5.00/pound and have ash level of less than 500 ppm in the carbonized insulation-grade fiber. Accordingly, a preliminary cost model was developed based on publicly available information. The team demonstrated that 4 lignin samples met the cost criteria. In addition, the ash level for the 4 carbonized lignin samples was below 500 ppm. Processing as-received lignin to produce a high purity lignin fiber was a significant accomplishment in that most industrial lignin, prior to purification, had greater than 4X the ash level needed for this project, and prior to this work there was not a clear path of how to achieve the purity target. The lab scale development of LBCF was performed with a specific functional application in mind, specifically for high temperature rigid insulation. GTI is a consumer of foreign-sourced pitch and rayon based carbon fibers for use in its high temperature insulation products, and the motivation was that LBCF had potential to decrease costs and increase product competitiveness in the marketplace through lowered raw material costs, lowered energy costs, and decreased environmental footprint. At the end of this project, the Technology Readiness Level (TRL) remained at 5 for LBCF in high temperature insulation.

09 BIOMASS FUELS↗

Conus-Wide Mapping of Water Availability and Cost

Background: New demands for water can be satisfied through a variety of source options. In some basins surface and/or groundwater may be available through permitting with the state water management agency (termed unappropriated water), alternatively water might be purchased and transferred out of its current use to another (termed appropriated water), or non-traditional water sources can be captured and treated (e.g., wastewater). The relative availability and cost of each source are key factors in the development decision. Unfortunately, these measures are location dependent with no consistent or comparable set of data available for evaluating competing water sources. With the help of water managers, water availability was mapped for over 2500 watersheds throughout CONUS. These values are unique in that they account for institutional factors (i.e., water rights, compacts, treaties, instream flows) that locally limit water use. Five water sources were individually examined, including unappropriated surface water, unappropriated groundwater, appropriated water, municipal wastewater and brackish groundwater. Associated costs to acquire, convey and treat the water, as necessary, for each of the five sources were estimated. These metrics were developed to support regional water planning and policy analysis with initial application to electric transmission planning in the western US. Problem: These data were originally developed in 20141 and updated in 20182. New datasets on which these data depend have been published. As such, there is need to update the water availability and cost data. There is also need to map this same data to a county resolution and to publish the data in a more accessible place. Organization of the dataset: Data are organized according to five primary water sources: • Unappropriated fresh surface water • Unappropriated fresh groundwater • Appropriated water • Recycled wastewater, and • Brackish water

Tidwell, Vincent [Pacific Northwest National Labor↗

Resource inventory for multi-agency watershed planning

A demonstration study showed that NASA high-altitude color infrared (RB-57) imagery is useful for providing timely, relatively inexpensive, and accurate land-use information. The inventory encompassed 18 land-use categories for a 2590-square-kilometer Michigan watershed. The RB-57 photography was compared to alternative data collection methods (including ERTS and Skylab) and was found to have superior cost effectiveness for providing the desired information.

Enslin, W. R.↗

TERSSE. Definition of the total earth resources system for the shuttle era. Volume 10: (TOSS) TERSSE operational system study

Economic benefits studies regarding the application of remote sensing to resource management and the Total Earth Resources for the Shuttle Era (TERSSE) study to outline the structure and development of future systems are used, along with experience from LANDSAT and LACIE, to define the system performance and economics of an operational Earth Resources system. The system is to be based on current (LANDSAT follow-on) technology and its application to high priority resource management missions, such as global crop inventory. The TERSSE Operational System Study (TOSS) investigated system-level design alternatives using economic performance as the evaluation criterion. As such, the TOSS effort represented a significant step forward in the systems engineering and economic analysis of Earth Resources programs. By parametrically relating engineering design parameters, such as sensor performance details, to the economic benefit mechanisms a new level of confidence in the conclusions concerning the implementation of such systems can be reached.

Stow, W. K.↗

Interagency comparison of iodometric methods for ozone determination

The California Air Resources Board appointed an Oxidant Calibration Committee for the purpose of evaluating the accuracy of the different agency calibration procedures. The committee chose UV absorption photometry as the reference method for ozone measurement. Interagency comparisons of the various iodometric methods were conducted relative to the ultraviolet standard. The tests included versions of the iodometric methods as employed by the Air Resources Board, the Los Angeles Air Pollution Control District, and the EPA. An alternative candidate reference method for ozone measurement, gas phase titration, was also included in the test series.

Demore, W. B.↗

Extended performance solar electric propulsion thrust system study. Volume 2: Baseline thrust system

Several thrust system design concepts were evaluated and compared using the specifications of the most advanced 30- cm engineering model thruster as the technology base. Emphasis was placed on relatively high-power missions (60 to 100 kW) such as a Halley's comet rendezvous. The extensions in thruster performance required for the Halley's comet mission were defined and alternative thrust system concepts were designed in sufficient detail for comparing mass, efficiency, reliability, structure, and thermal characteristics. Confirmation testing and analysis of thruster and power-processing components were performed, and the feasibility of satisfying extended performance requirements was verified. A baseline design was selected from the alternatives considered, and the design analysis and documentation were refined. The baseline thrust system design features modular construction, conventional power processing, and a concentractor solar array concept and is designed to interface with the space shuttle.

Poeschel, R. L.↗

Mars - Wind streak production as related to obstacle type and size

The characteristics of wind streaks associated with Martian craters and hills in the size range of 100 m to 80 km (corresponding to obstacle heights of a few to several hundred meters) have been analyzed from Viking Orbiter images. Both dark erosional and bright depositional streaks form over the entire obstacle size range, but there are preferred obstacle sizes for producing streaks. Bright streaks form more readily in association with relatively smaller obstacles than do dark streaks. Small obstacles produce both types of streaks more effectively than do large ones. Hills produce streaks as effectively as do craters of comparable height. Alternative explanations of bright streak formation are evaluated in terms of their ability to account for these observations. The most satisfactory models invoke blocking of atmospheric flow downwind of an obstacle and consequent deposition of dust within the sheltered zone.

Lee, S. W.↗

Speed benefits of tilt-rotor designs for LHX

The merits of an advanced helicopter and a tilt rotor aircraft for light utility, scout, and attack roles in combat missions envisioned for the year 2000 and beyond were compared. It is demonstrated that speed has increasing value for 11 different mission classes broadly encompassing the intended LHX roles. Helicopter speeds beyond 250 knots are judged to have lower military worth. Since the tilt rotor concept offers a different cost speed relationship than that of helicopters, assessment of a tilt rotor LHX variant was warranted. The technical parameters of an advanced tilt rotor are stablished. Parameters of representative missions are identified, computed relative value of the tilt rotor LHX are compared to the baseline helicopter, a first-order life cycle estimate for the tilt rotor LHX is established, military worth of the alternative design is computed and the results are evaluated. It is suggested that the tilt rotor is the solution with the greatest capability for meeting the uncertainties of future needs.

Mcdaniel, R. L.↗

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