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At least 775 records · Page 43

Affinity of LDR Organics to Cementitious Materials: Sorption and Leaching Tests

SRNL is working to identify and test the physiochemical interactions of organic contaminants of potential concern with minerals in grout/cementitious materials. Organic species may interact with cementitious minerals including slag, fly ash, cement, and other components/dopants like carbon in fly ash. The identification of such interactions will support the solidification process design, performance assessments for the chemicals of concern, and a proposed Resource Conservation and Recovery Act (RCRA) treatment variance specified for the Land Disposal Restriction (LDR) organics associated with Hanford tank waste. Inably expected to be present LDR organics associated with Hanford tank waste (RPP-RPT-63493, Rev 1a) was screened by functional groups, octanol-water partitioning coefficients, and detection frequency in Hanford tank waste samples. A subset of 10 compounds, spanning the identified properties, were tested using sorption and leachate tests. These compounds were subjected to traditional batch sorption tests and leaching tests on/from Cast Stone cementitious material with and without activated carbon (a potential organic adsorption additive). The interactions between organic compounds were observed in traditional batch sorption and modified Toxic Characteristic Leaching Procedure (TCLP) leachate tests for a surrogate Cast Stone material with and without an activated carbon addition. Specifically, phthalic acids (negatively charged) and 4-chloroaniline (polar) sorbed strongly to unmodified Cast Stone and a group of 3 phenolic compounds (2,4,6-Trichlorophenol, Pentachlorophenol, o-Cresol) were sorbed to and were retained by Cast Stone with a 1% activated carbon amendment.

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Affinity and Treatment of LDR Organics in Low Activity Waste by Cementitious Materials – 26109

The physiochemical interactions between organic contaminants, minerals, and polymer additives in grout/cementitious materials are being identified. This research supports a proposed Resource Conservation and Recovery Act (RCRA) treatment variance relevant to the Land Disposal Restriction (LDR) organics present in Hanford tank waste. It provides the technical basis to address the aspects documented by the Environmental Protection Agency in a draft memo necessary to establish that organics can be immobilized/stabilized in a cementitious matrix. The organic species may interact with cementitious minerals, including slag, fly ash, cement, and other components/dopants like activated carbon. A list of 132 reasonably expected LDR organics associated with Hanford tank waste (RPP-RPT-63493, Rev 1a) was screened by functional groups, octanol-water partitioning coefficients, and detection frequency in Hanford tank waste samples. A subset of 15 compounds spanning the identified properties was tested using sorption and leachate tests. These compounds were subjected to traditional batch sorption tests and leaching tests on/from Cast Stone cementitious material with and without activated carbon (a potential organic adsorption additive). The interactions between organic compounds were observed in traditional batch sorption and modified TCLP leachate tests for surrogate Cast Stone material with and without activated carbon addition. Specifically, phthalic acid (negatively charged) and 4-chloroaniline (polar) sorbed strongly to unmodified Cast Stone, while a group of three phenolic compounds (2,4,6-Trichlorophenol, Pentachlorophenol, o-Cresol) sorbed to and were retained by Cast Stone with a 1% activated carbon amendment. Mixtures of these compounds demonstrated visible retention of the organics within the matrix with a quantifiable affinity of the organics to the cement. This novel testing supports the notion that organics within Hanford tank waste would be retained onto the cement phase with the addition of simple materials easily added to the formulation as part of the treatment process. To further provide additional support to this claim, models employing Flory-Huggins theory in conjunction with macromolecular and organic molecule solubility parameters and species activity coefficients are being utilized to better understand these interactions. Within this context, Van Krevelen (VK) and Hansen organic and polymer solubility parameters were used to inform the Flory-Huggins interaction parameter, allowing for a quantifiable method of evaluating polymer-solvent compatibility and, by extension, interactions with proposed binding additives (e.g., activated carbon). These models and measurement should test the hypothesis for our systems understanding and applicability of Flory-Huggins theory, and whether the prediction of organics in the polymer phase versus the aqueous phase can be confidently made using this strategy. The estimation of the organic molecular activity coefficient in these high salt-saturated aqueous systems is another factor that will be assessed. This project aims to predict and understand complicated organic interactions in these heterogenous systems, guiding optimal treatment and stabilization methodologies.

Jolin, Will [Savannah River National Laboratory (S↗

Bioregenerative technologies for waste processing and resource recovery in advanced space life support system

The Controlled Ecological Life Support System (CELSS) for producing oxygen, water, and food in space will require an interactive facility to process and return wastes as resources to the system. This paper examines the bioregenerative techologies for waste processing and resource recovery considered for a CELSS Resource Recovery system. The components of this system consist of a series of biological reactors to treat the liquid and solid material fractions, in which the aerobic and anaerobic reactors are combined in a block called the Combined Reactor Equipment (CORE) block. The CORE block accepts the human wastes, kitchen wastes, inedible refractory plant materials, grey waters from the CELLS system, and aquaculture solids and processes these materials in either aerobic or anaerobic reactors depending on the desired product and the rates required by the integrated system.

Chamberland, Dennis↗

Conversion, Stability, and Selectivity Improvements Through Catalyst Development for the Reductive Etherification Reaction

Economical pathways from lignocellulosic non-food biomass feedstocks to biofuels with appropriate fuel properties are necessary for displacing fossil-fuel derived diesel use in medium-/heavy duty vehicles. Oxygenated compounds have recently shown promise due to low sooting tendencies and autoignition properties and molecules with sufficiently high carbon numbers can meet the requisite standards for water solubility and flash point. Coupling waste biomass derived small molecules into bioblendstock targets through the reductive etherification reaction shows potential for increasing molecular weight without losing the advantages of oxygenates. However, the transition to industrial viability for this process is limited by strong catalyst deactivation in typical flow reactor systems. Strong acid resins such as Amberlyst-15 (A-15) show excellent activity in batch reactions but are limited to low temperatures and are poisoned by the side-product, water. In this talk, I will describe our recent work in catalyst synthesis and testing to select superior options with improved aqueous and thermal stability in reductive etherification flow reactions. Water-tolerant solid acid catalysts have potential to improve the conversion and selectivity to the ether target at temperatures above the degradation point of A-15. Analysis techniques such as physisorption, chemisorption, x-ray diffraction and transmission electron microscopy are being used to characterize the active sites. These techniques are also being used to evaluate degradation of the catalyst after extensive flow reactions in addition to comparative efficiency testing with standardized cyclohexene hydrogenation reactions. Finally, I will discuss a demonstration of the full pathway from bio-derived butyric acid to the performance-advantaged ether product and the additional obstacles from side-products and purification limitations in the preliminary upgrading reactions.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

Update to the Performance Assessment for the Savannah River Site Saltstone Disposal Facility - 20124

In 2019, Savannah River Remediation developed a revision to the performance assessment (PA) on behalf of the U.S. Department of Energy (DOE) Savannah River Operations Office (SR) for the near-surface disposal of low-level waste at the Savannah River Site (SRS) Saltstone Disposal Facility (SDF). Soluble waste from SRS Tank Farms undergoes salt processing to remove cesium and other high activity constituents. The low-activity decontaminated salt solution (DSS) is then immobilized by mixing it into a cementitious waste form known as saltstone. After mixing, the saltstone is poured into leak-tight concrete vaults, known as saltstone disposal units (SDUs), where the waste form cures. By the time of facility closure, the SDF is expected to consist of 15 SDUs with a combined capacity of 1.06 E+09 L (280 Mgal) of cured saltstone. The facility operates under a Disposal Authorization Statement (DAS) from DOE and a permit from the South Carolina Department of Health and Environmental Control (SCDHEC). Since the start of operations in 1990, the SDF has received almost 6.7 E+07 L (18 Mgal) of DSS, resulting in the safe disposal of 2.7 E+16 Bq (7.3 E+05 Ci) of activity. Due to the radioactive decay of short-lived contaminants, the total remaining activity in the disposed waste is estimated to be approximately 1.4 E+16 Bq (3.9 E+05 Ci), as of September 2018. The Disposal Authorization Statement requires a demonstration that the system of engineered and natural features of the disposal facility will limit releases from the facility and be protective of human health and the environment for at least the next 1,000 years. The long-term performance of the facility was evaluated under the requirements of the DoE's Radioactive Waste Management Manual (US DOE Manual 435.1-1). Simulations were performed to demonstrate that the disposal facility would meet performance objectives specified in the manual. The evaluation was based on numerical models that simulate the releases of contaminants from the saltstone waste form. Contaminants were transported through groundwater and air pathways to points of assessment to evaluate compliance. In addition, the potential consequences of an inadvertent human intrusion (IHI) were also evaluated. In accordance with the guidance and recommendations in US DoE's technical standard for DAS, deterministic and probabilistic analyses were performed to demonstrate the SDF system, which includes the engineered cover system, the SDUs, the waste form, and the natural features of the site, provides a reasonable expectation that saltstone disposal will meet performance objectives. Post-closure doses to future members of the public (MOP) were evaluated; dose estimates from the air pathway were well below the 1.0 E-04 Sv/yr (10 mrem/yr) performance objective within 1,000 years, and the calculated doses to the MOP from all exposure pathways, including the groundwater and air pathways, were well below the 2.5 E-04 Sv/yr (25 mrem/yr) performance objective within 1,000 years. Doses following an assumed intrusion event within the facility boundaries were well below the IHI performance objectives, where the acute IHI dose was below the acute IHI dose performance objective of 5.0 E-03 Sv (500 mrem) and the chronic IHI dose was below the chronic IHI dose performance objective of 1.0 E-03 Sv/yr (100 mrem/yr) within 1,000 years. (author)

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Modeling of Solid Waste Processing Options in BIO-Plex

BIO-Plex is a ground-based test bed currently under development by NASA for testing technologies and practices that may be utilized in future long-term life support missions. All aspects of such an Advanced Life Support (ALS) System must be considered to confidently construct a reliable system, which will not only allow the crew to survive in harsh environments, but allow the crew time to perform meaningful research. Effective handling of solid wastes is a critical aspect of the system, especially when recovery of resources contained in the waste is required. This is particularly important for ALS Systems configurations that include a Biomass Production Chamber. In these cases, significant amounts of inedible biomass waste may be produced, which can ultimately serve as a repository of necessary resources for sustaining life, notably carbon, water, and plant nutrients. Numerous biological and physicochemical solid waste processing options have been considered. Biological options include composting, aerobic digestion, and anaerobic digestion. Physicochemical options include pyrolysis, SCWO (supercritical water oxidation), various incineration configurations, microwave incineration, magnetically assisted gasification, and low temperature plasma reaction. Modeling of these options is a necessary step to assist in the design process. A previously developed top-level model of BIO-Plex implemented in MATLAB Simulink (r) for the use of systems analysis and design has been adopted for this analysis. Presently, this model only considered incineration for solid waste processing. Present work, reported here, includes the expansion of this model to include a wider array of solid waste processing options selected from the above options, bearing in mind potential, near term solid waste treatment systems. Furthermore, a trade study has also been performed among these solid waste processing technologies in an effort to determine the ideal technology for long-term life support missions.

Rodriguez, Luis F.↗

PORFLOW Modeling of Vadose Zone Flow and Transport for the E- Area Low Activity Waste Vault

In support of the E-Area Performance Assessment, a two-dimensional model of water flow and radionuclide transport through the E-Area Low Activity Waste Vault (LAWV) and local vadose zone has been developed using the PORFLOW TM software. The purpose of the model is to calculate flux to the water table for radionuclides eluted from the LAWV during its operational life, the period of institutional control, and times following site closure. Results of model calculations will be used by a three-dimensional PORFLOW model of transport through the aquifer to determine radionuclide concentrations at a hypothetical 100 meter well and at the site boundary where contaminated groundwater could be accessed by members of the public following site closure.

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Hydrolysis Reaction Pathways of Thorium Oxide Nanoclusters

Density functional theory benchmarked by correlated molecular orbital theory is used to develop a fundamental and predictive understanding of the interaction of thorium oxide nanoclusters with gas phase water to provide insight into nuclear-waste storage, production of thorium nuclear reactor fuels, and reprocessing of spent fuel. The structures of Th n O 2n (n = 3 – 6) clusters and their interactions with water have been studied at the B3LYP, MP2, and CCSD(T) levels. Hydrolysis is initiated by the formation of Lewis acid-base adducts, with relative H 2 O binding energies (physisorption) ranging from −15 kcal/mol to −22 kcal/mol. The initial H 2 O physisorption energy is ca. −21 kcal/mol regardless of the cluster size and is consistent with the experimentally obtained initial adsorption energy on a thorium dioxide surface. The physisorption enthalpies for additional water molecules can be affected by the presence of terminal groups OH groups generated by proton transfer to a Th-O near the site of adsorption. The hydrolysis products (chemisorption) form either bridging or terminal hydroxides. More exothermic hydrolysis steps were predicted for the formation of terminal hydroxides as compared to the formation of bridging hydroxides. Here, the calculated transition state barriers for transfer of protons from bound water complexes to form the chemisorption products are very low. Overall, water readily reacts with thorium oxide clusters preferring hydroxide products over hydrated complexes. First and second order fits were predicted for the combined physisorption and chemisorption energies for the hydrolysis of thorium oxide clusters. Finally, ionization energies and electron affinities were calculated as were HOMO-LUMO gaps to provide additional insights into the properties of the thorium oxide and hydroxide clusters.

Adsorption↗

Development of a prototype experiment for treating CELSS and PCELSS wastes to produce nutrients for plant growth

Future long term spaceflights require extensive recycling of wastes to minimize the need for resupplying the vessel. The recycling occurs in a fully or partially closed environment life support system (CELSS or PCELSS). The National Aeronautics and Space Administration (NASA) is interested in converting wastewater into potable water or water for hydroponic farming as part of a CELSS. The development of technologies for wastewater treatment that produce a minimum of by-products is essential. One process that achieves good conversion of moderately concentrated organic wastes in water (1 to 20% by weight) completely to carbon dioxide and water is oxidation in supercritical water. Both air (or oxygen) and many organics are completely miscible with supercritical water, so there are no interphase mass transport resistances that limits the overall oxidation reaction. The temperature of supercritical water, which must be above 374 C, is also sufficient to have rapid reaction kinetics for the oxidations.

Source record↗

Modeling Stress-Induced Pore Water Pressures in The Vadose Zone Beneath a Composite-Lined Landfill - 20029

A finite-element model was developed to evaluate mechanisms contributing to positive pore pressures measured with sealed pressure transducers in the geological buffer beneath the Environmental Management Waste Management Facility, a composite-lined mixed waste disposal facility operated by the US Department of Energy. The geological buffer is a 3-m-thick engineered fine-textured layer directly beneath the Environmental Management Waste Management Facility's composite liner, and above the groundwater table. The model accounts for changes in pore water pressure resulting from (i) loading imposed by waste placed on the overlying liner, (ii) moistening of the geological buffer due to equilibration with the underlying geological materials, and (iii) fluctuations in the elevation of the underlying groundwater table. Pore water pressures predicted by the model are in good agreement with pore water pressures measured in the field. The predictions confirm that positive pore water pressures recorded by the sealed pressure transducers in the geological buffer are excess pore water pressures induced by the vertical normal stress imposed by waste placed on the liner, and are not due to a rise in the groundwater table. Simulations also showed that two additional years of filling would further increase the pore water pressure without any change in elevation of the groundwater table. The geological buffer remained unsaturated during the simulation, with a B-coefficient (parameter indicative of the degree of saturation) similar to that computed from the field-measured pore water pressures and waste filling records. Larger increases in pore water pressure were observed when the geological buffer was assumed to have higher initial saturation, as was observed in the field data. Incorporating seasonal fluctuations in the groundwater table beneath the geological buffer in the model resulted in predictions of small seasonal oscillation in the pore water pressure at the measurement location, similar to seasonal oscillations observed in the field. Predictions made with the model indicate that the dissipation of the excess pore water pressures will occur over decades due to the low hydraulic conductivity of the geological buffer material. (authors)

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Site Ambient Temperatures and Operating Schedules for EIC - Utility CW Considerations

The heat dissipated by the EIC accelerator system and components is ultimately removed by the conventional water-cooling systems that will be ultimately dissipated the waste heat to the atmosphere. An estimated 45 MW of heat will be dissipated to water during full beam operation and that will need to be effectively rejected to the atmosphere. Approximately 50% of the heat is required to be rejected to a low temperature heat sink that cannot be achieved by an evaporative cooling tower during summer. To operate during these summer months, a secondary chilled water refrigeration system will be required that would increase the cost of the cooling water system. Further, operating chiller compressor in the summer months will increase the energy consumption of the machine. This analysis is being prepared to evaluate the impact on operating and capital costs on the cooling system for various summer operating schedules while utilizing the most cost-effective scenario of an evaporative cooling system. The technology selection for the various heat sinks is addressed in a separate write-up and are not expected to change the conclusions of this write-up.

43 PARTICLE ACCELERATORS↗

Mesofluidic Inline Separation for Produced Water Treatment: CRADA 537 [Abstract only]

The mesofluidic inline separation developed by PNNL represents an opportunity to remove a key barrier in the treatment of produced water: suspended solids that clog downstream operations to remove dissolved solids. The US alone produces over a trillion gallons of produced water each year, most of which is reinjected as a waste product. The impact from treating and reusing even a fraction of this water is immense as aquifers in the Midwest and elsewhere drying.

54 ENVIRONMENTAL SCIENCES↗

Control of Structural Hydrophobicity and Cation Solvation on Interlayer Water Transport during Clay Dehydration

Swelling clay hydration/dehydration is important to many environmental and industrial processes. Experimental studies usually probe equilibrium hydration states in an averaged manner and thus cannot capture the fast water transport and structural change in interlayers during hydration/dehydration. Using molecular simulations and thermogravimetric analyses, we observe a two-stage dehydration process. The first stage is controlled by evaporation at the edges: water molecules near hydrophobic sites and the first few water molecules of the hydration shell of cations move fast to particle edges for evaporation. The second stage is controlled by slow desorption of the last 1–2 water molecules from the cations and slow transport through the interlayers. The two-stage dehydration is strongly coupled with interlayer collapse and the coordination number changes of cations, all of which depend on layer charge distribution. Furthermore, this mechanistic interpretation of clay dehydration can be key to the coupled chemomechanical behavior in natural/engineered barriers.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Ultimate disposal of scrubber wastes

Part of the initial concern with using the wet scrubbers on the hypergolic propellants was the subsequential disposal of the liquid wastes. To do this, consideration was given to all possible methods to reduce the volume of the wastes and stay within the guidelines established by the state and federal environmental protection agencies. One method that was proposed was the use of water hyacinths in disposal ponds to reduce the waste concentration in the effluent to less than EPA tolerable levels. This method was under consideration and even in use by private industry, municipal governments, and NASA for upgrading existing wastewater treatment facilities to a tertiary system. The use of water hyacinths in disposal ponds appears to be a very cost-effective method for reduction and disposal of hypergolic propellants.

Cohenour, B. C.↗

Advanced Mineral Extraction and Water Processing: Application Development of Mesofluidic Separation Technology

This project explored the development of mesofluidic devices and methods to provide a range of new capabilities with a focus on selective mineral extraction and cost-effective water treatment systems. Mineral separation and water treatment technologies are typically slow, bulky, expensive, time and energy intensive processes. This leads to very large, expensive processing plants that are often inefficient and produce low quality products and large volumes of waste. Technologies used in mineral extraction and water treatment have changed little in the last 50-100 years. The new technology, based upon mesofluidic separation devices, could disruptively change the state of the art and alter long established economics. The new technologies explored will provide systems with much smaller footprints, higher throughput, modular components easily integrated into existing industrial processes and plants, lower cost, and novel separation capabilities. The results from this effort contributed to a wide range of new capabilities and numerous inventions disclosures.

42 ENGINEERING↗

Water Walls for Life Support

A method and associated system for processing waste gases, liquids and solids, produced by human activity, to separate (i) liquids suitable for processing to produce potable water, (ii) solids and liquids suitable for construction of walls suitable for enclosing a habitat volume and for radiation shielding, and (iii) other fluids and solids that are not suitable for processing. A forward osmosis process and a reverse osmosis process are sequentially combined to reduce fouling and to permit accumulation of different processable substances. The invention may be used for long term life support of human activity.

Flynn, Michael T.↗

A Decade of Innovative Approaches to Treating and Dispositioning Radioactive Waste at the Savannah River Site - 20620

This year marks the 70. anniversary of the U.S. Department of Energy's (DOE) Savannah River Site (SRS), located near Aiken, South Carolina. SRS is a key industrial complex responsible for environmental stewardship, environmental cleanup, waste management, and disposition of nuclear materials. SRS also continues to have a role in critical defense-related activities and the reprocessing of used reactor fuel. The SRS encompasses 803 square kilometers (310 square miles) in parts of Aiken, Barnwell, and Allendale counties. The Liquid Waste Mission starts with the safe receipt and storage of radioactive liquid waste in the waste tanks, which principally includes Cold War legacy waste, but also waste from support of National Aeronautics Space Administration missions, medical isotope production, and research activities. This 133,000 cubic meters (m{sup 3}) (35 million gallons [Mgal]) of high-level radioactive waste (HLW) is currently held in 43 large underground waste tanks. The capacity of each of these tanks range from 2,800 m{sup 3} to 5,000 m{sup 3} (0.75 to 1.33 Mgal) and were placed in operation between 1954 and 1986. In July 2009, the DOE awarded a stand-alone contract to execute the Liquid Waste Mission at SRS. The Liquid Waste Contractor selected was Savannah River Remediation LLC1 (SRR), which is responsible for receipt, storage, retrieval and treatment of all HLW, disposal of the decontaminated low-activity waste fraction, as well as operationally closing cleaned HLW tanks. Since July 2009, SRR has successfully grouted and operationally closed six large underground tanks, poured 1,476 canisters of vitrified HLW (a stable glass waste form), treated approximately 34,200 m{sup 3} (9.0 Mgal) of HLW, and dispositioned over 41,200 m{sup 3} (10.9 Mgal) of decontaminated salt solution as low-level waste (LLW) into the Saltstone Disposal Units (SDUs) being constructed by SRR on site. The innovative work performed by SRR in the LLW portion of its mission has earned it the Richard S. Hodes Award. The work conducted by SRR is the same work championed by the late Richard S. Hodes, a respected physician, statesmen, and Chairman of the Southeast Compact Commission for Low-Level Radioactive Waste Management. (authors)

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Borehole Disposal of Radioactive Waste in Israel - 20388

Israel is assessing borehole disposal of radioactive waste. With limited geological options for disposal, intermediate-depth borehole disposal is being considered in the arid Yamin Plain region of the northeastern Negev desert at depths of several hundred meters below ground surface in the vadose zone. Unlike deep borehole disposal of several kilometers, which relies on emplacement below the depth of recirculating groundwater, the safety case for intermediate-depth borehole disposal relies more on the aridity of the vadose zone, the robustness of the waste package, and the other engineered barriers (e.g., seals, backfill materials) in the disposal borehole. As a tradeoff, the shallower depth may allow the use of a larger diameter borehole than would be possible for a deeper borehole. To study the suitability of the Yamin Plain region for borehole disposal, a small-diameter characterization borehole is being planned to retrieve core samples and to better understand the vadose zone geomechanical and hydrogeochemical properties and percolation flux. The information from the characterization borehole will inform the safety case, and together with performance assessment analyses will help to identify key areas of uncertainty and guide future research and development activities aimed at demonstrating the feasibility of the intermediate-depth borehole disposal concept in Israel. (authors)

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