SEARCH · Engineering Papers

Results for “Contamination Control Process”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

SourceResearch connectionFrom yearThrough year

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 397 records · Page 22

All sources NASA NTRS DOE OSTI

DOE OSTI2019

Ion exchange selectivity in clay is controlled by nanoscale chemical–mechanical coupling

Ion exchange in nanoporous clay-rich media plays an integral role in water, nutrient, and contaminant storage and transport. In montmorillonite (MMT), a common clay mineral in soils, sediments, and muds, the swelling and collapse of clay particles through the addition or removal of discrete molecular layers of water alters cation exchange selectivities in a poorly understood way. Here, we show that ion exchange is coupled to the dynamic delamination and restacking of clay layers, which creates a feedback between the hydration state of the exchanging cation and the composition of the clay interlayer. Particles with different hydration states are distinct phases with unique binding selectivities. Surprisingly, equilibrium achieved through thermal fluctuations in cation concentration and hydration state leads to the exchange of both ions and individual MMT layers between particles, a process we image directly with high-resolution transmission electron microscopy at cryogenic conditions (cryo-TEM). We introduce an exchange model that accounts for the binding selectivities of different phases, which is likely applicable to many charged colloidal or macromolecular systems in which the structural conformation is correlated with the activities of water and counterions within spatially confined compartments.

Whittaker, Michael L.↗

DOE OSTI2015

SPINE: SParse eIgengene NEtwork linking gene expression clusters in Dehalococcoides mccartyi to perturbations in experimental conditions

We present a statistical model designed to identify the effect of experimental perturbations on the aggregate behavior of the transcriptome expressed by the bacterium Dehalococcoides mccartyi strain 195. Strains of Dehalococcoides are used in sub-surface bioremediation applications because they organohalorespire tetrachloroethene and trichloroethene (common chlorinated solvents that contaminate the environment) to non-toxic ethene. However, the biochemical mechanism of this process remains incompletely described. Additionally, the response of Dehalococcoides to stress-inducing conditions that may be encountered at field-sites is not well understood. The constructed statistical model captured the aggregate behavior of gene expression phenotypes by modeling the distinct eigengenes of 100 transcript clusters, determining stable relationships among these clusters of gene transcripts with a sparse network-inference algorithm, and directly modeling the effect of changes in experimental conditions by constructing networks conditioned on the experimental state. Based on the model predictions, we discovered new response mechanisms for DMC, notably when the bacterium is exposed to solvent toxicity. The network identified a cluster containing thirteen gene transcripts directly connected to the solvent toxicity condition. Transcripts in this cluster include an iron-dependent regulator (DET0096-97) and a methylglyoxal synthase (DET0137). To validate these predictions, additional experiments were performed. Continuously fed cultures were exposed to saturating levels of tetrachloethene, thereby causing solvent toxicity, and transcripts that were predicted to be linked to solvent toxicity were monitored by quantitative reverse-transcription polymerase chain reaction. Twelve hours after being shocked with saturating levels of tetrachloroethene, the control transcripts (encoding for a key hydrogenase and the 16S rRNA) did not significantly change. By contrast, transcripts for DET0137 and DET0097 displayed a 46.8±11.5 and 14.6±9.3 fold up-regulation, respectively, supporting the model. This is the first study to identify transcripts in Dehalococcoides that potentially respond to tetrachloroethene solvent-toxicity conditions that may be encountered near contamination source zones in sub-surface environments.

59 BASIC BIOLOGICAL SCIENCES↗

DOE OSTI2015

Land-use planning scenarios for contaminated land: comparing EPA, state, and tribal scenarios - 15642

Land-use planning focusing on future disposition of public lands, forests and, former agricultural or industrial land, must take into account demographic and economic factors as well as future needs and availability of recreational open space, arable land, and water for growing populations. Planning requires the balancing of competing interests for 'growth', open space, and preservation of cultural, ecological and natural resources Landscapes with soil, surface water, and groundwater contaminated by former military, industrial, mining or agricultural uses, pose special challenges, many of which have been addressed under the rubric of 'brown-fields'. Land-use decisions or recommendations can be based mainly on economic/social interests taking into account projected demographic changes, or they can be based mainly on environmental issues taking into account contamination levels, remediation costs and technologies, and health risk issues. Future land-use is interwoven with cleanup goals. Where unrestricted future land-use is anticipated or desired, cleanup levels for soil and groundwater must be low enough to allow such uses without unacceptable health risks. Where such cleanup levels are unattainable for fiscal or technological reasons, residual contamination will remain, and future uses, particularly for groundwater, must be restricted, requiring engineered barriers and institutional controls to interdict future exposure pathways from contaminated environmental media to receptors (residents, recreationists, employees). Although contamination and hazard may persist for centuries, planning beyond a generation or two incurs great uncertainties in demographics, policies, economic, and climate-related changes. The Environmental Protection Agency and various states have established categories of clean-up levels corresponding to future industrial, recreational and residential use, with variations on these themes. This paper examines the spectrum of land-uses, and emphasizes a distinctions between -residential- and -unrestricted- as applied to future land-uses, particularly involving groundwater. Land-use determinations can be proposed and evaluated by a myriad of regulatory policies, guidance documents, and processes, including comprehensive land-use planning documents, Baseline Risk Assessments, Remedial Investigation/Feasibility documents and Records of Decision - which are not the focus of this study. This study instead focuses on gradations in different residential, recreational and industrial land-use scenarios and their relation to contamination of soil and groundwater. The Consortium for Risk Evaluation with Stakeholder Participation (CRESP) instituted this study to help understand the varying land-use versus clean-up decisions at the Department of Energy's environmental management sites, particularly Hanford (Washington State). (authors)

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2020

MH-1A Sturgis Decommissioning and Dismantlement - 20281

The U.S. Army Corps of Engineers (USACE) with its prime contractor, Aptim Federal Services, LLC (APTIM), recycled 5,260 metric tons (11.6 million pounds) of material from Sturgis Barge (Sturgis) during the Decommissioning and Dismantlement of the MH-1A nuclear power reactor. The overall objective of the project was to reduce residual radioactivity associated with MH-1A to levels that permitted release of Sturgis for dismantlement and termination of the Army Reactor Office permit. By effectively applying waste hierarchy's three Rs - reduce, reuse and recycle - the Sturgis project not only minimized the amount of waste that required disposal at landfills, but also reduced the potential for long-term environmental liability emanating from these landfills. The project team completed the physical decommissioning efforts in June 2018 in Galveston, TX. In September 2018, radiological surveys were completed to demonstrate the vessel could be released for shipbreaking. Sturgis was towed from Galveston, TX to Brownsville, TX in late September 2018. Shipbreaking, dismantlement and recycling efforts began in early October 2018 and were completed on 15 March 2019. As part of the decommissioning effort in Galveston, the team shipped 69 shipments (860 metric tons) of low-level radioactive waste and radioactive components to the Waste Control Specialist (WCS) facility in Andrews TX for disposal. Certain radioactive components had to be transferred to the Department of Energy prior to placing the materials into the Federal Waste Facility located within WCS. However, most of the radioactive waste was characterized, profiled, approved and managed under the WCS permitted radioactive waste exemption process authorized and implemented by the Texas Commission on Environmental Quality (TCEQ) and the Radioactive Materials Division. This allows LLRW and LLMW to be shipped as regulated waste and then upon receipt at WCS through satisfying the relevant waste acceptance criteria the waste is exempted and placed into the WCS RCRA permitted cell. An additional 35 shipments (544 metric ton) of contaminated hazardous waste water were transported to U.S. Ecology in Robstown, TX for treatment/disposal. An additional 36 shipments (500 metric tons) of non-hazardous wastewater was sent to Republic Waste Services' facility in Fresno, TX. The disposal of these materials required close coordination with State of Texas regulators. During decommissioning, the project team recycled approximately 270 metric tons (600,000 pounds) of lead and steel. As part of the dismantlement in Brownsville, TX the team recycled approximately 5,000 metric tons (11 million pounds) of ferrous and non-ferrous material, limiting our disposal requirements to about 180 metric tons (400,000 pounds) of material (<4% from entire shipbreaking activity). Although the primary hazard being mitigated by this project was radiological, recycling was always a priority for the project. The team strived to achieve sustainability goals as we implemented this one of a kind project. Scrap metal recycling has a large positive impact on the environment and can also favorably impact project disposal costs. Steel is among the most recycled material in the world. Nearly 40% of the world's steel production is made from scrap. Recycling steel also requires 75% less energy than producing it from raw materials. By using recycled steel rather than virgin materials, 2.33 kg of carbon emissions are eliminated per kg of steel [1]. The project recycled more than 4,500 metric tons (10 million pounds) of steel, which eliminated about 10,400 metric tons (23 million pounds) of CO{sub 2}. By implementing a recycling initiative for the Sturgis project, the team was able to realize cost avoidance for disposal of scrap, cost savings from the metals recycled, plus the project provided benefits to the environment through our recycling efforts. Once the dismantlement was complete, the team prepared a detailed decommissioning closure report, which allowed for the termination of the Army Reactor Decommissioning Permit. While it not only reduced any potential long-term environmental liability, this project to decommission and dismantle a floating nuclear power plant is truly unprecedented - it is a prime example of the USACE mission which is: 'Engineering solutions for the Nation's toughest challenges'. This unique, one of a kind, historical power plant was never designed to be taken apart, and the available information about its construction was lacking in many details. The hazards that required mitigation dictated a painstaking and deliberate process in order to avoid any release to the environment and the community, and to protect the health and safety of the workers involved while keeping the waste hierarchy's three R's - reduce, reuse and recycle at the forefront. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2023

AN ACID BAKING APPROACH TO ENHANCE RARE EARTH ELEMENT RECOVERY FROM BITUMINOUS COAL SOURCES

Rare earth elements (REE) are a group of 17 elements typically classified as light and heavy rare earth elements, which play a crucial role in developing the latest technologies for energy, defense, and medical sectors. Even though REEs have been found in more than 200 minerals, only bastnaesite, monazite and xenotime are commercially exploited for REE extraction. However, the recent exponential increase in REE demand has spurred countries such as the United States into research for the extraction of REEs from secondary sources such as coal, acid mine drainage, and coal ash. Several coal sources (e.g., Fire Clay seam coal) across the United States have been identified to contain elevated concentrations of rare earth elements (>600 ppm), and various researchers have investigated the feasibility of both physical and hydrometallurgical extraction techniques for rare earth concentration and subsequent extraction. However, both physical and direct leaching were concluded to be inefficient for RE beneficiation and extraction due to low recoveries. Alternatively, thermal treatment provides promising means for RE recovery from bituminous coal sources. The positive impact of thermal treatment/calcination was established to be due to the decarbonization and dehydroxylation of the clays, which released entrapped rare earth elements within the dominant minerals and converted them into an acid-soluble form. Nonetheless, the improvement in recovery was limited to the light REEs (LREEs) with an insignificant increase in the heavy REEs (HREE). It was demonstrated that the light and heavy REEs in the material were associated with difficult-to-leach minerals such as monazite, xenotime, and zircon, which were not decomposed by simple calcination due to their high thermal stability. Hence, roasting in the presence of chemicals was necessary to ensure the decomposition of those REE-containing minerals. As such, this study was focused on the acid baking treatment of bituminous coals with an aim to enhance REE recovery, especially HREEs. Based on the presence of REE minerals like monazite and xenotime, three pre-leach treatment methods, i.e., 1) roasting, 2) direct acid baking, and 3) acid baking after roasting were investigated. Roasting tests at 600 ⁰C revealed that the recovery of light REEs (LREEs) was enhanced while the recovery of HREEs remained relatively unaffected. LREE and HREE recovery values of 38.3% and 21.3%, respectively, were achieved using a 50 g/L sulfuric acid solution at 5% solid concentration and a solution temperature of 75 ⁰C for 2 hours. Comparatively, direct acid baking at 250 °C provided substantial increased LREE and HREE recovery values to approximately 49.4% and 53.0%, respectively, using an equivalent acid dosage. Recoveries were maximized to 77.0% and 79.6% for LREE and HREE, respectively, by roasting followed by acid baking. Similar results were obtained from the treatment of a second bituminous coal source. Due to strong correlations between REE and Al recovery values, tests were performed on kaolinite and illite, which were prominent clay minerals within the source coals. These experiments revealed that the REE recovery improvements were likely a result of dehydroxylation of clays and subsequent release and decomposition of REE-bearing minerals such as monazite, xenotime and zircon. Subsequently, a parametric study was conducted to identify the impact of acid baking parameters on rare earth element recovery. The factors investigated using a three-level statistical experimental program were acid baking time, acid solution concentration, baking temperature, and acid solution-to-solids ratio which were found to significantly impact REE and contaminant element (Al, Fe, and Ca) recovery. An increase in baking temperature up to around 250 ⁰C improved the light and heavy REE recovery values by more than 50 absolute percentage points relative to performances achieved when direct leaching. As aforementioned, acid baking was needed to both decompose the clay minerals and liberate the REE minerals, which allowed access for the acid to solubilize the REEs. Acid concentration of the solution used for acid baking was studied as a means of minimizing the amount of acid needed to achieve a target REE recovery. However, thermo-gravimetric and differential scanning calorimetry analysis (TGA-DSC) of sulfuric acid under oxidizing atmosphere revealed that the addition of water decreased the evaporation temperature, which explains the lower REE recovery values obtained when using acid concentrations less than 100%. Using pure sulfuric acid at an acid-to-solid ratio of 0.8:1 resulted in recovery values of around 70% for both LREEs and HREEs. The decomposition reaction time was relatively quick with 65% of the TREEs recovered within the first 10 minutes. Following the identification of optimum operating conditions through the parametric study, a systematic leaching study was carried out to examine the impact of leaching parameters, such as solid-to-liquid (S/L) ratio, temperature, and time, on REE recovery using acid baking conditions of 1:1 acid to solids ratio at 250 °C for 30 minutes. The solid-to-liquid ratio was varied from 1-20% by weight at 25 °C, 50 °C, and 75 °C solution temperatures. The results indicated that reaction time and solution temperature considerably impacted the recovery of heavy and light REEs. Interestingly, LREE recovery reduced from 68% at 5% S/L to 58% at 20%S/L, whereas HREE recovery of 78% remained unaffected. The decrease in the LREE recovery was determined to be due to La and Ce precipitation, likely through isomorphic substitution with calcium in gypsum. The kinetic data indicated that 67% LREE and 77% HREE recovery could be obtained within the first 15 minutes of the reaction, suggesting fast reaction kinetics. Furthermore, raising the solution temperature from 25 °C to 75 °C increased the LREE and HREE recovery from 60% and 32% to 67% and 79%, respectively. The kinetic modeling results demonstrated that the rate-limiting step in the LREE dissolution was diffusion and chemical reaction, whereas the HREE extraction was controlled by only chemical reaction. The leaching study concluded that using 20% S/L at 75 °C for 15 minutes maximized LREE and HREE recovery. The lab-scale precipitation study showed that Fe and Al in solution could be removed at pH 4.5 followed by REE precipitation at pH 6.0 using 6 mol/L NaOH. Finally, the bench-scale data was used to develop a process flowsheet for REE recovery from low-grade bituminous coal sources using acid baking. Finally, based on the proposed flowsheet, a concentrated RE-cake obtained through selective precipitation at pH 6.5 was re-leached using HCl at pH 1.5. The resultant leachate was used to identify the impact of various operating parameters on REE recovery and purity with an aim to maximize REE precipitation efficiency while minimizing the oxalic acid dosage. The operating parameters for this investigation were oxalic acid dosage, iron (III) contamination, solution pH and temperature. The resultant model suggested that oxalic acid dosage and reaction pH are the most significant factors for the REE precipitation efficiency, followed by the interaction of oxalic dosage and Fe concentration. Test results indicated that increasing the oxalic acid concentration from 0g/L to 80g/L improved the REE precipitation efficiency from approximately 4.2% to 95.0%. Furthermore, raising the solution pH from 0.5 to 2.5 considerably enhanced the precipitation efficiency from 0.0% to 98.9%. A solution temperature elevation decreased REE recovery, which indicated an exothermic reaction between REEs and oxalate anions. Finally, a high level of Fe contamination adversely impacted REE precipitation efficiency. The speciation analysis revealed that the dominant iron species in the solution system were Fe-(C₂O₄)₃³⁻, Fe-(C₂O₄)²⁻, and Fe-(C₂O₄)⁺, which consumed the majority of the oxalate anions

rare earth elements, acid baking, high-temperature↗

DOE OSTI2017

Kinetics of Cation and Oxyanion Adsorption and Desorption on Ferrihydrite: Roles of Ferrihydrite Binding Sites and a Unified Model

Understanding the kinetics of toxic ion reactions with ferrihydrite is crucial for predicting the dynamic behavior of contaminants in soil environments. In this study, the kinetics of As(V), Cr(VI), Cu, and Pb adsorption and desorption on ferrihydrite were investigated with a combination of laboratory macroscopic experiments, microscopic investigation and mechanistic modeling. The rates of As(V), Cr(VI), Cu, and Pb adsorption and desorption on ferrihydrite, as systematically studied using a stirred-flow method, was highly dependent on the reaction pH and metal concentrations and varied significantly among four metals. Spherical aberration-corrected scanning transmission electron microscopy (Cs-STEM) showed, at sub-nano scales, all four metals were distributed within the ferrihydrite particle aggregates homogeneously after adsorption reactions, with no evidence of surface diffusion-controlled processes. Based on experimental results, we developed a unifying kinetics model for both cation and oxyanion adsorption/desorption on ferrihydrite based on the mechanistic-based equilibrium model CD-MUSIC. Overall, the model described the kinetic results well, and we quantitatively demonstrated how the equilibrium properties of the cation and oxyanion binding to various ferrihydrite sites affected the adsorption and desorption rates. Our results provided a unifying quantitative modeling method for the kinetics of both cation and oxyanion adsorption/desorption on iron minerals.

Environmental Molecular Sciences Laboratory↗

DOE OSTI2020

Contaminant Migration Modeling to Support the In Situ Decommissioning of Hardened Nuclear Facilities - 20215

The decommissioning of hardened nuclear facilities provides a unique challenge in balancing current worker dose with exposure to future receptors and media. In situ decommissioning (ISD) is a cost-effective and safe option for the closure of such facilities but requires a detailed understanding of the threat that radioactive and hazardous constituents remaining in the facilities pose to groundwater and surrounding surface water. The Savannah River Site (SRS) extensively employs contaminant migration models within the decommissioning process to develop site-specific removal, grouting, and monitoring strategies in support of safe and effective final end states of nuclear facilities. This work discusses the use of contaminant migration modeling in the ISD process at SRS, including specific examples from the closure of P-Reactor and R-Reactor, Building 235-F, F-Canyon and F/H Laboratory Complex. Migration models developed during the closure of P-Reactor and R-Reactor were divided into four source areas: the reactor vessel, the process area, the disassembly basin, and the purification wing. Each source area was assigned a specific inventory and migration pathway and was then subject to varying hypothetical removal, capping, and grouting schemes. Modeling indicated that groundwater Maximum Concentration Limits (MCLs) might be exceeded if no action was taken for eleven and ten constituents of concern (COCs) at P-Reactor and R-Reactor, respectively. These exceedances could occur in as few as 200 to 500 years. Alternatively, the migration modeling demonstrated that the selected ISD actions reduced contaminant mobility which allowed for significant radioactive decay and resulted in fewer predicted exceedances of groundwater MCLs (five COCs for P-Reactor; eight COCs for R-Reactor). In response to the modeling results for P-Reactor and R-Reactor, effectiveness monitoring programs were developed to target contaminants, specific to each reactor, that may migrate to groundwater. Contaminant migration modeling also revealed that roof collapse was a large factor in the release of COCs to the environment, giving rise to roof improvements, and an inspection and vegetation control program to ensure roof stability over time. Contaminant migration modeling is also aiding in the closure planning for hardened facilities in F Area. Building 235-F housed the Actinide Billet Line, which produced Np-237 billets for irradiation in SRS reactors, and the Plutonium Fuel Form (PuFF) facility that produced Pu-238 heat sources for the space program. As a result of these missions, areas within Building 235-F contain considerable residual amounts of both Pu-238 and Np-237. Contaminant migration modeling of Building 235-F was originally performed in 2012 to identify the feasibility of ISD and the amount of radioactive material removal required to prevent the exceedance of groundwater MCLs. The original model indicated that a 60% reduction in the PuFF facility Pu-238 inventory could keep groundwater concentrations below standards, while Np-237 did not pose a threat to groundwater. However, updates to the model with an emphasis on source impact pathways revealed that, due to the orientation of the source areas relative to groundwater flow, no amount of reasonable removal of Pu-238 would keep groundwater concentrations below MCLs and that Np-237 could be a large contributor to localized MCL exceedances. With this insight, the refined 2019 model is being used to assist in the development of grouting plans specific to each facility source area, where bentonite may be utilized to slow the migration of Pu-238 and its daughter products from the PuFF facility and a reducing grout may decrease Np-237 transport by ensuring the nuclide remains in the less mobile +IV oxidation state. The beginning phases of contaminant migration modeling are underway for F-Canyon and associated facilities using lessons learned from the Reactors and Building 235-F. A contaminant migration pathway, similar to the pathway used for the reactor vessels, is being developed for the hot and warm canyons. The F-Canyon inventories are being spatially refined to identify specific and localized source zones, comparable to Building 235-F, that may impact groundwater. Contaminant migration modeling provides vital input within the ISD process, from facility investigation to post closure effectiveness monitoring, making it a valuable tool in the development of safe and effective end states for hardened nuclear facilities at SRS. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2013

Single-faced GRAYQB™: a radiation mapping device

GrayQb{trademark} is a novel technology that has the potential to characterize radioactively contaminated areas such as hot cells, gloveboxes, small and large rooms, hallways, and waste tanks. The goal of GrayQb{trademark} is to speed the process of decontaminating these areas, which reduces worker exposures and promotes ALARA considerations. The device employs Phosphorous Storage Plate (PSP) technology as its primary detector material. PSPs, commonly used for medical applications and non-destructive testing, can be read using a commercially available scanner. The goal of GrayQb{trademark} technology is to locate, quantify, and identify the sources of contamination. The purpose of the work documented in this report was to better characterize the performance of GrayQb{trademark} in its ability to present overlay images of the PSP image and the associated visual image of the location being surveyed. The results presented in this report are overlay images identifying the location of hot spots in both controlled and field environments. The GrayQb{trademark} technology has been mainly tested in a controlled environment with known distances and source characteristics such as specific known radionuclides, dose rates, and strength. The original concept for the GrayQb{trademark} device involved utilizing the six faces of a cube configuration and was designed to be positioned in the center of a contaminated area for 3D mapping. A smaller single-faced GrayQb{trademark}, dubbed GrayQb SF, was designed for the purpose of conducting the characterization testing documented in this report. This lighter 2D version is ideal for applications where entry ports are too small for a deployment of the original GrayQb™ version or where only a single surface is of interest. The shape, size, and weight of these two designs have been carefully modeled to account for most limitations encountered in hot cells, gloveboxes, and contaminated areas. GrayQb{trademark} and GrayQb{trademark} SF share the same fundamental detection system design (e.g., pinhole and PSPs). Therefore, performance tests completed on the single face GrayQB in this report is also applicable to the six- faced GrayQB (e.g., ambient light sensitivity and PSP response). This report details the characterization of the GrayQb{trademark} SF in both an uncontrolled environment; specifically, the Savannah River Site (SRS) Plutonium Fuel Form Facility in Building 235-F (Metallurgical Building) and controlled testing at SRS’s Health Physics Instrument Calibration Facility and SRS’s R&D Engineering Imaging and Radiation Systems Building. In this report, the resulting images from the Calibration Facility were obtained by overlaying the PSP and visual images manually using ImageJ. The resulting images from the Building 235-F tests presented in this report were produced using ImageJ and applying response trends developed from controlled testing results. The GrayQb{trademark} technology has been developed in two main stages at Savannah River National Laboratory (SRNL): 1) the GrayQb{trademark} development was supported by SRNL’s Laboratory Directed Research and Development Program and 2) the GrayQb{trademark} SF development and its testing in Building 235-F were supported by the Office of Deactivation and Decommissioning and Facility Engineering (EM-13), U.S. Department of Energy – Office of Environmental Management.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

DOE OSTI2023

Exploratory Synthesis for Reactive f-Element Separations without Solvent

Solvent extraction is commonly used to separate different f-metals found in spent nuclear fuel, but this process results in large volumes of highly contaminated liquid waste that must be remediated or stored at significant expense. The project funded under this award was aimed at addressing solvent-related issues encountered in conventional f-metal separations. Our strategy focused on using solvent-free mechanochemical reactions to prepare lanthanide and actinide borohydride complexes so that they could be separated based on differences in their volatility. Key deliverables described in this report include proof-of-principle results demonstrating that borohydrides called aminodiboranates can be used for volatile lanthanide/lanthanide and lanthanide/uranium separations, as we proposed. Moreover, exploration of a closely related class of borohydrides called phosphinodiboranates allowed us to identify underlying chemical factors that control the volatility of trivalent lanthanide and uranium borohydride complexes with identical structures. Details of published and pending research products are provided, and these include comprehensive synthesis and characterization efforts required to support fundamental studies related to the proposed separations. These technical efforts supported the training of nine graduate students and three undergraduate researchers, and they established air-sensitive transuranic capabilities at the University of Iowa to enhance radiochemical workforce development.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2024

Exploratory Synthesis for Reactive f-Element Separations without Solvent

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

DOE OSTI2020

Sustaining On-going Risk Communication at the Riverton, Wyoming, Processing Site - 20310

An environmental risk assessment report has been completed to provide an updated assessment regarding current site conditions for the Riverton, Wyoming, Processing site. Argonne National Laboratory conducted the assessment in collaboration with the U.S Department of Energy (DOE) Office of Legacy Management (LM) and the Northern Arapaho Natural Resources Office (NANRO). The data quality objectives process conducted confirmed that data from plants growing on the Riverton site would be useful and would address an outstanding concern. Data available from site soil, groundwater, and surface water were also used in the assessment in conjunction with the new plant data. A plant survey was then conducted in 2018 to identify the plants at the Riverton site with known traditional Native American cultural uses for sampling and analysis. Laboratory analysis was conducted on the plant samples for the contaminants of concern. Samples were collected from plants growing on the groundwater plume area of the site, and the same was done for eight other areas not affected by the groundwater plume but still within the institutional control boundary. These eight areas served as reference areas for this study. This human health and ecological assessment update provide the quantitative risk information that was qualitatively addressed in a 1995 Risk Assessment Report on plants, livestock, and surface water exposures at the Riverton site [1]. The conditions at the Riverton site are protective of human health and the environment given the results of the update, in combination with past completed remedial action and ongoing monitoring activities and IC implementation. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2020

Study of an Unrefined Humate Solution as a Possible Attenuation-based Remedy for Uranium Contamination in Acidic Groundwater - 20351

The Savannah River Site (SRS), joined the environmental cleanup program in 1981 after the Cold War, and was designated as a hazardous waste management facility. About 1.8 billion gallons of acid wastes were disposed into the F/H Area Seepage Basin that included many radionuclides and dissolved metals, resulting in highly contaminated groundwater plumes with pH of 3 - 5.5. The acidity of the plumes contributes to the mobility of several constituents of concern (COC) such as H-3, U-238, I-129, and Sr-90 for the F-Area plume and H-3, Sr-90 and mercury for the H-Area plume. An active treatment (pump-and-treat and re-injection) system was constructed and put in place in 1997 to address the removal of metals and radionuclides from the contaminated groundwater. As remediation projects advanced, active treatments were transitioned to more passive or enhanced-passive approaches such as the subsurface barrier with base injection system, which has been controlling the mobility of contaminants. However, new and more efficient attenuation-based remedies are always sought. Several studies have proposed that humic substances can be used to remediate sites contaminated with heavy metals by creating a permeable reactive barrier. Humic substances (HS) are major components of soil organic matter. HS are polyfunctional organic macromolecules formed by the chemo-microbiological decomposition of biomass or dead organic matter. These substances are usually divided into three main fractions: humin (insoluble at all pH values), humic acid (soluble at pH greater than 3.5), and fulvic acid (soluble at all pH values). Humic substances are major components of the soil at SRS and, in addition, are also helpful in the removal process of uranium. This research focuses on uranium (VI), which is a key contaminant of concern in the F-Area groundwater plume. The interaction of uranium with sediment in the presence or absence of humic substances involves complex mechanisms that are not yet well understood. The interaction of U(VI) with humic substances can affect the adsorption of U on sediment, altering its mobility in the subsurface. The objective of this study is to study the mobility of uranium in the presence of humic acid and to determine if sediments amended by humic acid can enhance the sorption of heavy metals onto sediments. In this research, experiments were conducted using background (clean) F-Area aquifer sediments to understand and predict uranium mobility. A blended material, humate, containing both humic and fulvic acids and a chemically modified humate (KW15 modified humic or mod-HA) was studied as a possible amendment for uranium remediation in SRS groundwater. Batch experiments were conducted in triplicates using 20 ml of aqueous suspension in DI water containing SRS sediment and mod-HA and studied the effect of pH, kinetics of humate sorption onto SRS sediment and also studied the sorption of uranium onto mod-HA amended SRS sediment. Results indicate that mod-HA amended sediment increases uranium removal significantly. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2022

National Ignition Facility. Facility and Infrastructure Systems Maintenance Plan

Ensuring the reliability of the NIF, including its support systems, laser systems, target diagnostic systems, and utilities, is essential to the availability of the NIF in its support of NNSA missions. NIF is a key capability in the DOE Stockpile Stewardship Program and supports high energy physics experiments for nuclear weapons, energy, and astrophysics applications. High system reliability provides opportunities for shots and scientific discoveries with opportunities to enhance and upgrade capabilities. This Maintenance Plan (MP) identifies the policies and procedures used to perform and support asset management of the NIF Facility and Infrastructure Systems (FInS), NIF Lasers & Alignment (LASE), NIF Target Experimental Operations (TOPS), NIF Target Area Science and Engineering (TASE), and NIF&PS Control Systems (NCS). The FInS systems include the facility, HVAC, contamination control, beampath, and Line Replaceable Units (LRUs) as well as utilities which create the beampath environments, such as vacuum, argon, or clean dry air. The LASE systems are Programmatic systems which include laser diagnostics, alignment, power conditioning, pulsed power, and input laser systems. The TOPS and TASE systems are also Programmatic systems which include target and diagnostic delivery systems and positioners, many different insertable and fixed target diagnostics, and cryogenic and target gas fill systems. Finally, the NCS systems include both software and hardware for industrial and shot operation control systems. Policies governing administrative and operational practices related to maintenance of FInS, LASE, TOPS, TASE, and NCS systems are described in this plan. In addition, the plan provides processes and procedures for managing, tracking, and documenting the work. This document, the NIF Operations Management Plan, NIF-5020544 (Ref. 1), and NIF Shot Operations Plan, NIF-5018506 (Ref. 2), together satisfy the requirements of the Conduct of Operations. Duties, responsibilities, and reporting requirements of the various positions associated with FInS, LASE, and TOPS maintenance are detailed in this plan. The FInS systems include both Real Property systems with asset management requirements specified in DOE Order 430.1C (Ref. 3) and Programmatic systems. In addition, for FInS, there is a list of the System Level Maintenance Plans (SLMPs) in NIF-1007419198 (Ref. 4) which provide the system descriptions and maintenance plan and schedule. In addition, the list includes the Reliability Centered Maintenance (RCM) and Experience Centered Maintenance (ECM) evaluations that have been performed for applicable FInS systems as well as reliability criticality per Section 3.5. The -AM version of the NIF Maintenance Plan focuses on the reliability program for FInS, LASE, TOPS, TASE, and NCS within the context of the overall NIF Reliability, Availability, and Maintainability (RAM) program and incorporates changes since the -AL version from August 2011 and has been updated to be fully consistent with the updates to Ref. 1. It also includes asset management considerations, updates to the Work Order (WO) process within the NIF Computerized Maintenance Management System (CMMS) which is EAM infor® System Maintenance and Reliability Tracking (SMaRT) (Ref. 5), and updates to metrics and key performance indicators (KPIs).

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

DOE OSTI2019

Phosphate amendments for chemical immobilization of uranium in contaminated soil

Uranium (U) contamination is a major environmental problem associated with the mining and processing of nuclear materials for both weapons and power production. When possible, in situ soil remediation techniques are preferable for reducing the risk associated with diffuse low-level U contamination. Uranium is known to form sparingly soluble phosphate compounds that persist in the environment. Therefore, batch experiments were performed to evaluate the efficacy of three phosphate amendments, hydroxyapatite (HA), sodium phytate (IP6) and sodium tripolyphosphate (TPP), to immobilize U in contaminated sediments. The amendments were added at equivalent phosphorus (P) concentrations and then equilibrated under a range of test conditions, with changes in soluble U and Ptotal monitored at pre-set time intervals. Only HA was effective at reducing the soluble U soil fraction when compared to the control, with IP6 and TPP increasing the soluble U soil fraction. After equilibration, changes in contaminant partitioning in the amended sediments were evaluated using operational extraction methods. Sequential extraction results for HA generally indicated a transfer of U from labile to more recalcitrant phases, while the results for IP6 and TPP were more ambiguous.

Uranyl↗

DOE OSTI2016

Uranium-Bearing Evaporite Mineralization Influencing Plume Persistence. Literature Review and DOE-LM Site Surveys

This report on evaporite mineralization was completed as an Ancillary Work Plan for the Applied Studies and Technology program under the U.S. Department of Energy (DOE) Office of Legacy Management (LM). This study reviews all LM sites under Title I and Title II of the Uranium Mill Tailings Radiation Control Act (UMTRCA) and one Decontamination and Decommissioning site to provide (1) a summary of which sites have evaporite deposits, (2) any available quantitative geochemical and mineralogical analyses, and (3) references to relevant reports. In this study, “evaporite” refers to any secondary mineral precipitate that occurs due to a loss of water through evaporative processes. This includes efflorescent salt crusts, where this term refers to a migration of dissolved constituents to the surface with a resulting salt crust, where “salt” can refer to any secondary precipitate, regardless of constituents. The potential for the formation of evaporites at LM sites has been identified, and may have relevance to plume persistence issues. Evaporite deposits have the potential to concentrate and store contaminants at LM sites that could later be re-released. These deposits can also provide a temporary storage mechanism for carbonate, chloride, and sulfate salts along with uranium and other contaminants of concern (COCs). Identification of sites with evaporites will be used in a new technical task plan (TTP), Persistent Secondary Contaminant Sources (PeSCS), for any proposed additional sampling and analyses. This additional study is currently under development and will focus on determining if the dissolution of evaporites has the potential to hinder natural flushing strategies and impact plume persistence. This report provides an initial literature review on evaporites followed by details for each site with identified evaporites. The final summary includes a table listing of all relevant LM sites regardless of evaporite identification.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2019

H-Canyon Tunnel Inspection System

Cable Analysis: The crawlers is controlled remotely via a long coax cable. In order to make sure we do not damage the cable which could cut our contact (data/power/control), we had to determine the bend radius of it at certain locations. This was done with dimensional analysis in Creo and inputting the information into a MATLAB program. Engineering Drawings: Since many of the crawlers parts, such as the main body, needed to be machined, part drawings were needed to communicate the details necessary for manufacture. Project Overview: The H-Canyon Ventilation Exhaust Tunnel due both to its long service history and exposure to aggressive process offgas chemistry has experienced degradation. In order to allow visual inspection of the condition of the radioactively-contaminated tunnel, a remote crawler was designed to deliver cameras as needed to return high definition video. My involvement included Vendor Searches, Cable Analysis, Thermal Analysis, and Engineering Drawings. Thermal Analysis: In order to see if internal active cooling is needed for the crawler, simplified thermal models were designed to approximate the internal temperatures: Conduction (assumes all heat sources are thermally-coupled to the crawler body); Convection (assumes no heat sources are thermally-bonded to crawler). Going Forward: Continue refining the cable analysis as the crawler model is updated and refined. Use my knowledge gained here to further my skills in engineering.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2013

Application of Ultrasonic for Decontamination of Contaminated Soil - 13142

The trials of soil decontamination were carried out with the help of a pilot ultrasonic installation in different modes. The installation included a decontamination bath equipped with ultrasonic sources, a precipitator for solution purification from small particles (less than 80 micrometer), sorption filter for solution purification from radionuclides washing out from soil, a tank for decontamination solution, a pump for decontamination solution supply. The trials were carried out on artificially contaminated sand with specific activity of 4.5 10{sup 5} Bk/kg and really contaminated soil from Russian Scientific Center 'Kurchatovsky Institute' (RSC'KI') with specific activity of 2.9 10{sup 4} Bk/kg. It was established that application of ultrasonic intensify the process of soil reagent decontamination and increase its efficiency. The decontamination factor for the artificially contaminated soil was ∼200 and for soil from RSC'KI' ∼30. The flow-sheet diagram has been developed for the new installation as well as determined the main technological characteristics of the equipment. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2016

Efforts to Improve Efficiency of Extraction Well Operation at the Fernald Preserve, Harrison, Ohio – 16177

The Fernald Preserve, a former uranium processing facility that produced high-purity uranium metal products during the Cold War, is located in southwest Ohio. The facility became a US Department of Energy Office of Legacy Management (LM) site in November 2006, following completion of the Comprehensive Environmental Response, Compensation, and Liability Act environmental remediation and site restoration (with the exception of groundwater). When the site was turned over to LM, approximately 76.5 ha of the Great Miami Aquifer remained contaminated with uranium above the final remediation level of 30 μg/L. Here, uranium contamination is being removed from groundwater in the Great Miami Aquifer through a pump-and-treat operation, which is predicted to continue until 2033. Twenty extraction wells pump about 30 million liters per day. Operation of the system is impacted by iron in the groundwater that promotes iron fouling of the well pumps, motors, and screens. The design of the well field evolved over 21 years and reflected a conservative system that could respond to a wide range of pumping conditions. For instance, some of the extraction wells were sized with pumps and motors that would allow the well to pump up to 1890 L/min (500 gpm) if warranted. The added flexibility, though, came at the cost of operational efficiency. We describe the efforts that have been taken by LM since the Fernald site was transferred to LM to mitigate the operational impacts from the iron fouling aquifer conditions and improve the efficiency of the well-field operation. Variable-frequency drives were installed at six wells to replace flow control valves. Several wells with oversized pumps and motors were changed from 24-hour per day operation to 8-hour per day operation to allow the pumps to operate closer to their design flow rates. Pumps and motors were “right-sized” at many wells to improve pumping efficiency. The process used to rehabilitate (or clean) well screens was improved, and a process was developed to clean pumps without having to pull them from the well. To reduce pressure drops, improvements were also made to the configuration of the discharge piping. A new control system was installed for each well to allow local control and local tracking of energy used. The amount of energy used daily compared to number of gallons pumped provides a method to assess pump performance and determine when action is necessary to restore well pump efficiency. Additionally, the metrics being employed to help quantify well-field efficiency improvements are described, and the benefits achieved by proactively managing the pump-and-treat operation are presented.

54 ENVIRONMENTAL SCIENCES↗