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At least 271 records · Page 15

Saltstone Waste Characterization Analysis - Salt Waste Processing Facility (SWPF) Waste Stream (Q4 CY2020)

The Saltstone Production and Disposal Facility is designed and permitted by the state of South Carolina Department of Health and Environmental Control (SCDHEC) to treat and dispose of low-level radioactive and hazardous liquid waste (salt solution) remaining from the processing of radioactive material at the Savannah River Site (SRS). Low-level waste (LEW) aqueous streams from the Effluent Treatment Project (ETP) and decontaminated solutions from the Tank Closure Cesium Removal Unit (TCCR) and the Salt Waste Processing Facility (SWPF) are stored in Tank 50 until the LEW can be transferred to the Saltstone Facility for treatment and disposal. In the past, decontaminated solution from the Modular Caustic Side Solvent Extraction Unit (MCU) was stored in Tank 50 until the LEW could be transferred to the Saltstone Facility for treatment and disposal. MCU is currently in a suspended operations state. LEW that meets the Waste Acceptance Criteria (WAC) can be transferred, stored, and treated in the Saltstone Production Facility (SPF) for subsequent disposal as saltstone grout in the Saltstone Disposal Facility (SDF). Sampling will be conducted as new waste streams are identified for treatment and disposal at the Saltstone Industrial Wastewater Treatment Facility (IWTF) and Z-Area Industrial Solid Waste Landfill (ISWLF), Facility ID# 025500-1603, General Condition B.9 or every six years in accordance with South Carolina (SC) Regulation 61-107.19 Parti C, “Solid Waste Management: Solid Waste Landfills and Structural Fill - General Requirements.”

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Synthesis of an aqueous, air-stable, superconducting 1T'-WS 2 monolayer

Liquid-phase chemical exfoliation can achieve industry-scale production of two-dimensional (2D) materials for a wide range of applications. However, many 2D materials with potential applications in quantum technologies often fail to leave the laboratory setting because of their air sensitivity and depreciation of physical performance after chemical processing. We report a simple chemical exfoliation method to create a stable, aqueous, surfactant-free, superconducting ink containing phase-pure 1T'-WS 2 monolayers that are isostructural to the air-sensitive topological insulator 1T'-WTe 2 . The printed film is metallic at room temperature and superconducting below 7.3 kelvin, shows strong anisotropic unconventional superconducting behavior with an in-plane and out-of-plane upper critical magnetic field of 30.1 and 5.3 tesla, and is stable at ambient conditions for at least 30 days. Our results show that chemical processing can make nontrivial 2D materials that were formerly only studied in laboratories commercially accessible.

36 MATERIALS SCIENCE↗

Versatile coating with multifunctional performance for solar steam generation

In this work, a new kind of material, composite complex coating (CCC), with multifunctional performance has been developed for solar steam generation. The CCC has many advantages: (a) Scalability. The fabrication process is facile and mild; it can be realized in aqueous solution at room temperature, without high pressure, toxic organic solvents, or complex equipment. (b) Cost-effectiveness. The reagents used for preparation of CCC are low-cost and readily available. (c) Universality and stability. CCC firmly adheres on surfaces of various substrates with diverse shapes (cotton, filter paper, wood, polyurethane sponge, and even chemically inert and highly hydrophobic polyvinylidene fluoride membranes), and can withstand rinsing treatment (3000 r/min for 96 h), cyclic frost-thaw test (-18 °C ⇌ 30 °C, 90 times), and both high and low pH environments. In addition, many other reported coatings, such as carbon black, fail under similar process strain. (d) Anti-crude oil-fouling property. The CCC possesses stable superhydrophilicity and underwater superoleophobicity, which collectively endow substrates with the ability to resist fouling by oils. (e) Broad and strong light absorption. CCC can transform various substrates with diverse shapes into black materials with broadband light absorption due to its d-d transitions and rough surface. Together, these properties of CCC enable substrates with nearly any structural design to be easily transformed into photothermal materials for efficient solar steam generation. Furthermore, as a proof of concept, poplar wood is treated with CCC, achieving a water evaporation rate of ~1.8 kg m-2 h-1 (one sun), which is a record among wood-based photothermal materials.

14 SOLAR ENERGY↗

Abatement of radioiodine in aqueous reprocessing off-gas

The reprocessing used nuclear fuel (UNF) releases volatile fission and activation products, including 129 I, into the off-gas of a processing plant. Mitigation of the release of vapor phase radionuclides is necessary for meeting regulatory requirements in the United States and other countries. In an aqueous reprocessing plant, volatile radioiodine could be present in several forms, depending on the chemistry of the process used. Inorganic iodine will be the predominate species in any shearing or voloxidation pretreatment off-gas and dissolver off-gas (DOG). Organic iodides such as CH 3 I, C 4 H 9 I, and C 12 H 25 I have been proposed to be generated during solvent extraction; thus, these species must be captured from the vessel off-gas (VOG). The abatement of inorganic and organic iodide species to meet United States regulatory requirements has been demonstrated in laboratory experiments using Ag-based solid sorbents. The data presented in this paper includes the effect of gas composition (e.g., the presence of water vapor and NO x ), iodine speciation (I 2 , CH 3 I, C 4 H 9 I, C 12 H 25 I), and sorbent bed parameters (e.g., temperature, sorbent age) on complete iodine capture on Ag-mordenite in an aqueous reprocessing plant.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Probing the Mechanism of Selective Phosphate Adsorption from Wastewater Using Aqueous and Synchrotron X-ray Characterization

Ion exchange shows promise for recovering phosphate from wastewater as value-added products, but requires high phosphate selectivity to compete with conventional treatment. Hybrid anion exchange (HAIX) resins, which contain non-selective basic functional groups and selective iron oxide nanoparticles (FeOnp), can effectively remove phosphate from wastewater. However, knowledge gaps remain regarding the mechanisms of phosphate selectivity and influence of competing ions, hindering needed efforts to model adsorption dynamics and design scalable adsorption processes for varying wastewaters. To address these gaps, we integrated aqueous-phase adsorption analysis with solid-phase, synchrotron-based X-ray characterization; this integration facilitated elucidation of the distribution and speciation of iron, phosphate, and competing anions on HAIX resins. We compared a quaternary ammonium-functionalized HAIX resin (SBA) to a tertiary amine version (WBA) to determine the role of functional groups. X-ray radiography revealed differences in FeOnp speciation (goethite vs. ferrihydrite) and distribution (peripheral vs. homogeneous) between the resins, resulting in varied phosphate affinity and intraparticle diffusion resistance. Using micro-X-ray fluorescence (μ-XRF) and micro-X-ray absorption near-edge structure (μ-XANES) spectroscopy, we identified differences in where and how phosphate binds across resin types and wastewaters. Across wastewater compositions, FeOnp sites in WBA contribute more to phosphate adsorption than in SBA, possibly due to variations in Fe distribution and speciation. Phosphate adsorption densities calculated from quantitative μ-XRF maps matched those from aqueous analysis, demonstrating the effectiveness of this integrated approach. Altogether, results demonstrate the use of synchrotron-based X-ray characterization for investigating adsorption mechanisms and advance HAIX as a phosphate recovery technology from complex wastewaters.

Nutrient recovery↗

Accumulation of Antifreeze Proteins on Ice Is Determined by Adsorption

Antifreeze proteins (AFPs) enable the survival of organisms in freezing environments by binding to ice crystals and suppressing their growth. The rate at which AFPs accumulate on ice is determined by an interplay between their diffusion from the aqueous solution and their adsorption to the ice crystal. To interrogate the relative importance of these two processes, we combined fluorescence experiments with reaction–diffusion modeling. We found that as AFPs accumulate on ice, their concentration in the aqueous solution does not develop a gradient but remains equal to its bulk concentration throughout our experiments. Furthermore, these findings led us to conclude that AFP accumulation on ice crystals, which are smaller than 100 μm in radius, is not limited by the diffusion of AFPs, but by the kinetics of AFP adsorption.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Valorization of lignin from aqueous-based lignocellulosic biorefineries

An additional 100 million tons/year of lignin coproduct will result when lignocellulosic biomass is processed in biorefineries to fiber, sugars, biofuels, and bioproducts. This will double the amount of lignin already generated from pulping and paper production. Unlike pulping that results in lignosulphonate (88% of total) or Kraft lignin (9%), aqueous-based biorefining leaves behind non-sulfonated lignin and aromatic molecules. Furthermore, this new type of lignin provides opportunities for large volume agricultural uses such as controlled-release carriers and soil amendments as well as feedstocks for new chemistries that lead to molecular building blocks for the chemical industry and to precursors for sustainable aviation biofuels.

03 NATURAL GAS↗

Effective direct steam regeneration of bis-iminoguanidine solid sorbent used for carbon dioxide capture

A cost-effective, energy-efficient sorbent regeneration process for phase-changing guanidines used for CO 2 capture was developed based on direct-steam stripping. This approach enhances the regeneration rate, simplifies the overall CO 2 capture process, and reduces the energy cost compared to conventional conductive thermal regeneration. A direct-steam sorbent regeneration reactor was developed, demonstrating that aqueous bis(iminoguanidines) (BIG) sorbents, e.g., methylglyoxal-bis(iminoguanidine) (MGBIG) and glyoxal-bis(iminoguanidine) (GBIG), could be efficiently regenerated with up to ~ 99 % CO 2 recovery through direct-steam stripping. Using low-temperature steam at 100 °C, a 4.5 times faster regeneration rate for GBIG carbonate sorbent (e.g., 30 min for 10 g) was demonstrated compared to conductive-heating (e.g., 135 min for 10 g) at 130 °C. Additionally, fully regenerated MGBIG converts into an aqueous MGBIG solution when the steam condenses onto the sorbent surface. Condensed steam with the guanidine can be easily recycled as an aqueous solution into the gas–liquid contactor to achieve a continuous-flow CO 2 -capture process. Molecular dynamics simulation was employed to provide a better understanding of the process. Higher heat transfer rates from steam to guanidine carbonate, compared to air heating, were attributed to the vibration resonance of water molecules within MGBIG with that of vapor molecules and the effective transfer of kinetic energy from vapor to solid. Technoeconomic analysis demonstrated that direct-steam stripping significantly decreases the CO 2 capture cost by 50 % compared to traditional conductive heating methods. Further, enhanced mass transfer facilitated by low-temperature steam and subsequent condensation effectively heats up the H 2 O-containing BIG-carbonate crystals, facilitating the desorption of CO 2 from the solid crystals, thereby leading to fast, effective, and energy-efficient sorbent regeneration.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Mark-18A Cold Runs

The Savannah River National Laboratory (SRNL) is tasked by the National Nuclear Security Administration (NNSA) to recover highly valued isotopes from irradiated Mark-18A (Mk-18A) targets. The Savannah River Site (SRS) has sixty-five Mk-18A targets available for the recovery of the high valued materials. The sixty-five Mk-18A targets are currently stored in the L-Area Basin and will be removed one at a time and individually transported to SRNL. Upon receipt at SRNL, the Mk-18A target material will be removed from the confinement, dissolved, chemically separated, and calcined to a stable oxide. The flowsheet is designed to recover the plutonium as well as the trivalent actinides. The remaining unrecovered material will be discarded to the high activity drain (HAD) system in SRNL. A specially designed cask was procured for transport of the targets from L-Area to SRNL. Once received at SRNL, the targets will be loaded into the back of Cell 7 and resized as they enter the cell. The resized targets (1/4 lengths) will then be processed one at a time through the following processes: caustic dissolution and filtration; acidic dissolution and filtration, Reillex anion exchange, diglycolamide (DGA) cation exchange; and DGA calcination. This processing will result in two product streams. The first is an aqueous plutonium solution which will be removed from the shielded cells and taken to a glovebox for further purification and conversion to an oxide. The second is a calcined oxide containing the Am and Cm as well as other lanthanide fission products which will be removed from the shielded cells using a bagless transfer system. Both materials will be packaged for shipment to Oak Ridge National Laboratory (ORNL). All equipment to carry out this process was designed, procured or fabricated, and installed in a mock-up facility (716-4A) at SRS to allow for simulation testing in a non-radioactive area. This equipment was then dismantled and transferred from 716-4A to 773-A and installed in the SRNL Shielded Cells. After installation in the shielded cells facility testing was performed using water followed by surrogates and cold chemicals. Issues were identified during these evaluations, including equipment issues as well as technical challenges. Many of the issues were rectified during performance of the cold runs, and the remaining have a resolution identified. Table ES-1 provides a summary of all issues identified during the cold run operations, as well as the status and identified resolutions to outstanding issues.

07 ISOTOPE AND RADIATION SOURCES↗

Ion Exchange Processes for CO 2 Mineralization Using Industrial Waste Streams: Pilot Plant Demonstration and Life Cycle Assessment

Abstract An attractive technique for removing CO 2 from the environment is sequestration within stable carbonate solids (e. g., calcite). However, continuous addition of alkalinity is required to achieve favorable conditions for carbonate precipitation (pH>8) from aqueous streams containing dissolved CO 2 (pH<4.5) and Ca 2+ ions. In this study, a pH‐swing process using ion exchange was demonstrated to process 300 L of produced water brine per day for CO 2 mineralization. Proton titration capacities were quantified for aqueous streams in equilibrium with gas streams at various concentrations of CO 2 (pCO 2 =0.03–0.20 atm) and at various flow rates (0.5–2.0 L min −1 ). Energy intensities for the process were determined to be between 30 and 65 kWh per tonne of CO 2 sequestered depending on the composition of the brine stream. A life cycle assessment was performed to analyze the net carbon emissions of the technology which indicated a net CO 2 reduction for pCO 2 ≥0.12 atm (−0.06–−0.39 kg CO 2 e per kg precipitated CaCO 3 ) utilizing calcium‐rich brines. The results from this study indicate the ion exchange process can be used as a scalable method to provide alkalinity necessary for the capture and storage of CO 2 in Ca‐rich waste streams.

Chemistry↗

Nitrogen-doped char as a catalyst for wet oxidation of phenol-contaminated water

Catalytic wet oxidation (CWO) of aqueous effluents rich in organic compounds is a very promising technology for the treatment of liquid wastes from biomass conversion processes. CWO reactions occur through the formation of free radical species, produced in the presence of an oxidant, which act on organic contaminates in the effluent. Although the reaction is well known, there exists a lack of affordable catalysts to conduct this process at the lower temperatures and pressures in novel bioenergy processes. Here, this study assessed the catalytic effect of nitrogen-doped chars as such an option. Phenol in aqueous solution was used as a model waste effluent. Treatment was conducted at moderate temperatures (190 to 260 °C), oxygen partial pressure of 1 MPa, and reaction times of 15, 30, and 45 min in stainless steel and glass-lined tube reactors. High pressure liquid chromatography (HPLC) analyses of the products quantified phenol and by-product concentrations used in the calculation of reaction activation energy. The char catalyst was studied by X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), and scanning electron microscopy (SEM) in order to gain insight into its structure and surface composition. The results indicate that nitrogen-doped char catalysts accelerate the oxidation of phenol by decreasing its reaction activation energy from 82.2 kJ/mol (non-catalyzed) to 40.4 kJ/mol (catalyzed). An analysis from first principles using density functional theory (DFT) was conducted to ascertain which N functional group has the most significant impact on free radical formation in the presence of oxygen. Among all the N functional groups studied, the dipyridinic functional groups showed the most promising characteristics to facilitate the formation of hydroxyl free radicals.

Advanced Oxidation Processes for Organic Pollutant↗

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

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

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Photo-DAC: Light-Driven Ambient-Temperature Direct Air Capture by a Photobase

Direct air capture (DAC) may reduce atmospheric CO 2 concentrations to preindustrial levels, yet the high energies and temperatures involved in current DAC technologies hinder large-scale deployment. In the case of aqueous-based CO 2 absorbents, a large energetic penalty is associated with heating and boiling off water, as required for thermally driven solvent regeneration. This could be avoided via photochemically driven pH swings involving photoacids or photobases, and harnessing abundant and renewable solar energy, though efficient solvent regeneration and recycling in a realistic multicycle DAC process remains challenging. Herein, we report a photochemically driven DAC process (photo-DAC) in which atmospheric CO 2 capture by an aqueous glycylglycine (GlyGly) solution is enabled through a pH swing by a pyridine-substituted diiminoguanidine (PyDIG) photobase. Upon irradiation with UV light, the PyDIG photobase undergoes photoisomerization from the E,E to the Z,Z isomer, corresponding to a pK a increase of 2.8 units that activates GlyGly for DAC through deprotonation. After the GlyGly/PyDIG solvent is saturated with atmospheric carbon dioxide, leaving it in the dark under ambient conditions leads to the isomerization of PyDIG from the Z,Z back to the E,E isomer, which is accompanied by a pH drop and CO 2 release. To demonstrate the recyclability of the GlyGly/PyDIG solvent, we have completed six consecutive DAC cycles, with a measured average cyclic capacity in the range of 0.21–0.26 mol CO 2 per mol of GlyGly/PyDIG. These results open the prospect for energy-efficient DAC cycles completed entirely at ambient conditions, thereby avoiding the significant energy penalties associated with heating and boiling aqueous solvents.

Einkauf, Jeffrey D. [Oak Ridge National Laboratory↗

Unexpected Hydroxide Ion Structure and Properties at Low Hydration

Understanding the behavior of hydroxide ions in aqueous and non-aqueous media is fundamental to many chemical, biological, and electrochemical processes. Research has primarily focused on a single fully solvated hydroxide ion, either as an isolated cluster or in bulk. This work presents the first computational study to consider hydroxide under low hydration levels in detail, where the anion may not be fully solvated. Under such conditions, we find that the anions are predominantly present as unique water-bridged hydroxide pair complexes, distinct from previously reported structures under fully hydrated conditions. Although similar hydroxide pair structures were previously reported, we analyze these structures for the first time in the disordered liquid state where they are found to be unusually stable in the presence of bulky quaternary ammonium cations. Our findings help explain the unusual diffusion behavior as well as the higher reactivity of hydroxide anions observed under low hydration conditions.

computational studies↗

Synergistic and Antagonistic Effects of Aromatics on the Agglomeration of Gas Hydrates

Abstract Surfactants are often used to stabilize aqueous dispersions. For example, surfactants can be used to prevent hydrate particles from forming large plugs that can clog, and sometimes rupture pipelines. Changes in oil composition, however dramatically affect the performance of said surfactants. In this work we demonstrate that aromatic compounds, dissolved in the hydrocarbon phase, can have both synergistic and antagonistic effects, depending on their molecular structure, with respect to surfactants developed to prevent hydrate agglomerations. While monocyclic aromatics such as benzene were found to disrupt the structure of surfactant films at low surfactant density, they are expelled from the interfacial film at high surfactant density. On the other hand, polycyclic aromatics, in particular pyrene, are found to induce order and stabilize the surfactant films both at low and high surfactant density. Based on our simulation results, polycyclic aromatics could behave as natural anti-agglomerants and enhance the performance of the specific surfactants considered here, while monocyclic aromatics could, in some cases, negatively affect performance. Although limited to the conditions chosen for the present simulations, the results, explained in terms of molecular features, could be valuable for better understanding synergistic and antagonistic effects relevant for stabilizing aqueous dispersions used in diverse applications, ranging from foodstuff to processing of nanomaterials and advanced manufacturing.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Sustainable lead management in halide perovskite solar cells

Despite the rapid development of perovskite solar cells (PSCs) toward commercialization, the toxic lead (Pb) ions in PSCs pose a potential threat to the environment, health and safety. Managing Pb via recycling represents a promising approach to mitigating its toxicity. However, managing Pb from commonly used organic solvents has been challenging due to the lack of suitable Pb adsorbents. Here, we report a new adsorbent for both separation and recovery of Pb from PSC pollutants. The synthesized iron-incorporated hydroxyapatite possesses a strongly negatively charged surface that improves electrostatic interaction through surface-charge delocalization, thus leading to enhanced Pb adsorption. Finally, we demonstrate the feasibility of a complete Pb management process, including the purification of Pb-containing non-aqueous solvents below 15 parts per 10 9 , a level compliant with the standards of the US Environmental Protection Agency, as well as recycling of 99.97% of Pb ions by forming lead iodide.

14 SOLAR ENERGY↗

In vitro investigation of protein assembly by combined microscopy and infrared spectroscopy at the nanometer scale

The nanoscale structure and dynamics of proteins on surfaces has been extensively studied using various imaging techniques, such as transmission electron microscopy and atomic force microscopy (AFM) in liquid environments. These powerful imaging techniques, however, can potentially damage or perturb delicate biological material and do not provide chemical information, which prevents a fundamental understanding of the dynamic processes underlying their evolution under physiological conditions. Here, we use a platform developed in our laboratory that enables acquisition of infrared (IR) spectroscopy and AFM images of biological material in physiological liquids with nanometer resolution in a cell closed by atomically thin graphene membranes transparent to IR photons. In this work, we studied the self-assembly process of S-layer proteins at the graphene-aqueous solution interface. The graphene acts also as the membrane separating the solution containing the proteins and Ca 2+ ions from the AFM tip, thus eliminating sample damage and contamination effects. The formation of S-layer protein lattices and their structural evolution was monitored by AFM and by recording the amide I and II IR absorption bands, which reveal the noncovalent interaction between proteins and their response to the environment, including ionic strength and solvation. Our measurement platform opens unique opportunities to study biological material and soft materials in general.

59 BASIC BIOLOGICAL SCIENCES↗