Hanford Site Research Articles

Boron nitride: Novel ceramic reductant for low‐activity waste vitrification

AbstractDuring vitrification of radioactive wastes, excessive foaming reduces processing rates within melters by hindering heat transfer from the molten glass pool to the reacting melter feed. Formulations of low‐activity waste (LAW) melter feeds, for vitrification at the Waste Treatment and Immobilization Plant at the Hanford Site, conventionally include the addition of sucrose to mitigate excessive foaming by hastening the denitration process. However, incomplete combustion of sucrose produces organics such as acetonitrile (C2H3N) that may exceed bounding limits of downstream effluent treatment facilities. Using boron nitride (BN) as an alternate reductant to sucrose, in a representative LAW melter feed reduced C2H3N production by 90% by preventing the low‐temperature sucrose–nitrate reactions. Furthermore, foaming was suppressed due to the higher decomposition temperature of BN than H3BO3 meaning a delayed reaction of a large fraction of boron with the transient glass‐forming melt until above the foam onset temperature, thus reducing the quantity and viscosity of the connected melt and trapping less gas in the foam layer.

Using the National Land Cover Database as an indicator of shrub-steppe habitat: comparing two large United States federal lands with surrounding regions

ABSTRACT There is a need to assess whether ecological resources are being protected on large, federal lands. The aim of this study was to present a methodology which consistently and transparently determines whether two large Department of Energy (U.S. DOE) facilities have protected valuable ecological lands on their sites compared to the surrounding region. The National Land Cover Database (2019) was used to examine the % shrub-scrub (shrub-steppe) and other habitats on the DOE’s Hanford Site (HS, Washington) and on the Idaho National Laboratory (INL), compared to a 10-km and 30-km diameter band of land surrounding each site. On both sites, over 95% is in shrub-scrub or grassland, compared to the surrounding region. Approximately 70% of 10 km and 30-km bands around INL, and less than 50% of land surrounding HS is located in these two habitat types. INL has preserved a significantly higher % shrub/scrub habitat than HS, but INL allows grazing on 60% of its land. HS has preserved a significantly higher % grassland than INL but no grazing on site is present. The methodology presented may be used to compare key ecological habitat types such as grasslands, forest, and desert among sites in different parts of the country. This methodology enables managers, resource trustees, and the public to (1) make remediation decisions that protect resources, (2) assess whether landowners and managers have adequately characterized and protected environmental resources on their sites, and (3) whether landowners and managers have protected the integrity of that land as well as its climax vegetation.

Spectral induced polarization of corrosion of sulfur modified Iron in sediments

Spectral induced polarization (SIP) responses are not well understood within the context of remediation applications at contaminated sites. Systematic SIP studies are needed to gain further insights into the complex electrical response of dynamic, biogeochemical states to enable the use of SIP for subsurface site characterization and remediation monitoring. Although SIP measurements on zero valent iron have been previously published, the SIP response for sulfur modified iron (SMI), a similar potential subsurface reductive amendment, has not yet been reported. Hence, the purpose of this laboratory-scale study was to evaluate SIP for nonintrusive monitoring of SMI under relevant subsurface conditions. SMI was separately mixed with silica sand or sediments from the Hanford Site (Washington, USA) and then packed into columns for geochemical and SIP analysis for up to 77 days under fully saturated conditions. SMI exhibited distinguishable phase peaks between 0.1 and 1.0 Hz, which changed in magnitude based on content and were detected as low as 0.3 wt%. In the initial days, the complex conductivity, phase maxima, and chargeability increased while the peak locations shifted to higher frequency (decreasing relaxation times), suggesting an initial increase in polarization and concurrent decrease in the length scales (potentially due to changes in particle size and mineralogy). Then, after 77 days, the phase maxima and chargeability decreased with a concurrent increase in relaxation times, suggesting that over longer periods, less polarizable phases are forming and particle size or connectivity of polarizable phases is increasing. These results demonstrated a unique SIP response to SMI transformations that might be applied to monitoring of SMI emplaced as a subsurface barrier or injected in the field.

Sampling in Long-Screened Wells: Issues, Misconceptions, and Solutions.

The issues associated with long-screened wells (LSWs) (and open boreholes) at contaminated sites are well documented in the groundwater literature but are still not fully appreciated in practice. As established in seminal and review papers going back over three decades, the interpretation of sampling results from LSWs is challenging in the presence of vertical hydraulic gradients and borehole flow; furthermore, LSWs allow for vertical redistribution of contamination between aquifer layers. Acknowledgment of these issues has led to the development of new technologies and well designs to enable discrete-zone monitoring (DZM), yet LSWs remain common for many reasons, for example, as multipurpose wells, for geophysical logging, and (or) as legacy installations. Despite the literature on LSWs and despite the adoption of DZM at many sites, the use of LSWs persists and the challenges of interpreting sampling results from LSWs remain. In this issue paper, we provide a conceptual overview of the problems posed by LSWs and review existing literature and past work to improve the interpretation of sampling in LSWs. We draw on experience from previous studies at the Hanford Site in eastern WA, USA, and use synthetic examples to illustrate key concepts and challenges for interpretation. A recently published analytical modeling framework is used to develop illustrative synthetic examples and demonstrate a workflow for building scientific intuition to understand issues around interpreting samples from LSWs, which is critical to effective characterization and groundwater remediation at sites with LSWs.

Subsurface Transport of Plutonium in Organic and Aqueous Acidic Processing Wastes at the Hanford Site, USA.

Over 4 million liters of mixed acidic (∼pH 2.5), high ionic strength (∼5 M nitrate) plutonium (Pu) processing waste were released into the 216-Z-9 (Z-9) trench at the Hanford Site, USA, and trace Pu has migrated 37 m below the trench. In this study, we used flowthrough columns to investigate Pu transport in simplified processing waste through uncontaminated Hanford sediments to determine the conditions that led to Pu migration. In low pH aqueous fluids, some Pu breakthrough is observed at pH < 4, and increased Pu transport (14% total Pu breakthrough) is observed at pH < 2. However, Pu migrates in organic processing solvents through low pH sediments virtually uninhibited with approximately 94 and 86% total Pu breakthrough observed at pH 1 and pH 3, respectively. This study demonstrates that Pu migration can occur both with and without organic solvents at pH < 4, but significantly more Pu can be transported when partitioned into organic processing solvents. Our data suggest that under acidic conditions (pH < 4) in the vadose zone beneath the Z-9 trench, Pu present in organic processing solvents moved relatively unhindered and may explain the historical downward migration of Pu tens of meters below the Z-9 trench.

Automated SEM analysis of particles in Hanford tank waste

Multiple bench-scale filtration campaigns of Hanford tank waste supernatant on a backpulseable dead-end filtration skid have provided greater insight into the solids that cause fouling and reduce filter performance. The solids collected during each campaign were concentrated from the backpulse solutions and examined using automated particle analysis (APA) methods with scanning electron microscopy and X-ray energy dispersive spectroscopy to categorize particle types and their morphological characteristics. We show that with APA, thousands of particles can be analyzed to provide accurate insight into the phases that may be impacting filter performance.

Long-Term Performance of Ag/AgCl Reference Electrodes for Corrosion Potential Monitoring in Radioactive Tank Waste at the Hanford Site

This work studied the exposure effects of radioactive tank waste on the long-term performance of single junction Ag/AgCl reference electrodes for corrosion potential monitoring at the Hanford Site. Electrodes from three manufacturers with very different designs were studied using open-circuit potential and electrochemical impedance measurements in radioactive tank waste. Post-test analyses were conducted on some failed electrodes using destructive and nondestructive techniques. The intrusion of the aggressive and radioactive chemicals in tank waste through the porous frit materials was the primary mechanism that led to the clogging of frit, physical and chemical degradation of AgCl bonded to Ag wire, and alteration of the internal electrolyte. Radiolytic chemical species such as H2O2 and HNO3 may have also induced the degradation of the Ag wire. The extent of electrode degradation and failure probability highly depended on the electrode design and environmental conditions. Chemicals in tank waste had stronger effects than radiation on the long-term performance of the Ag/AgCl reference electrodes.

Glass design using machine learning property models with prediction uncertainties: Nuclear waste glass formulation

The United States Department of Energy is responsible for managing the legacy nuclear waste stored in underground tanks at the Hanford Site. The waste will be separately vitrified as low-activity waste and high-level waste fractions. Waste glass formulation algorithms have been traditionally developed using partial quadratic mixture property-composition models. Recently, machine learning (ML) techniques have been used to predict glass properties and discover new glass materials for nuclear waste vitrification, and these advancements can be utilized to improve waste glass composition design. In this proof-of-principle study, ML algorithms such as Gaussian process regression (GPR) were used to interpolate glass properties (e.g., viscosity, electrical conductivity, chemical durability). After selecting appropriate sets of GPR hyper-parameters for each property, an optimization program was developed to formulate glass compositions to maximize waste loading while simultaneously satisfying property constraints. The results of the ML-based waste loadings and glass compositions were compared to those obtained using the traditional methods. Comparing to the previous glass design framework, the ML-based optimization methods offer improved glass designs and a streamlined approach to generation of optimally designed data and near real-time updates.

Effect of ion penetration on the aging of EPDM components used in caustic liquid transfer lines by microscopic analysis

The waste transfer lines at the United States Department of Energy's Hanford Site Tank Farm in Benton County, Washington, USA have flexible sections that are fabricated from ethylene propylene diene monomer (EPDM) hoses. The hoses are of a hose-in-hose design with an inner hose that carries the waste and an outer hose that acts as containment in the event of an inner hose failure. During waste transport, the inner hoses are exposed to several stressors including caustic solutions at high temperatures and high pressures. These hose-in-hose transfer lines (HIHTL) are exposed to several stressors including caustic solutions at high temperatures and high pressures during the waste transport. The aging behavior of the HIHTL inner hose were evaluated by exposure to solutions at 77 °C containing 6.25, 12.50, and 25.00% (v/v) sodium hydroxide (NaOH) for 12-months. After the exposure, the burst pressure of the HIHTL specimens were measured and compared to the unaged samples.The burst pressure of the HIHTL specimens exposed to the 6.25% NaOH solution exhibited the most significant deterioration and those exposed to 25.00% NaOH solution had the least deterioration. Examination of the inside surface of the HIHTL specimens with scanning electron microscopy showed that the surface deterioration for the specimens exposed to 6.25% NaOH solution were the most severe and the samples exposed to 25.00% NaOH solution had the least deterioration. Scanning Electron Microscope with Energy Dispersive Spectroscopy (SEM-EDS) analysis of the specimens showed that the specimen aged with the 6.25% NaOH solution had that greatest sodium ion penetration into the material with the sodium concentration being significantly higher than those seen with the other specimens. In addition, when the specimens aged with both the 12.50% and the 25.00% NaOH solutions were examined, a white crystalline coating was observed on the inside surfaces of the specimens which appears to have acted as a barrier that protected the EPDM material from attack by the NaOH solutions.

Long-Term Performance of Reference Electrodes in Alkaline Radioactive Waste Storage Environments

Accurate measurements of corrosion potential are important for assessing the likelihood of internal localized corrosion and stress corrosion cracking of carbon steel tanks used for storing radioactive wastes. Reference electrodes in underground radioactive waste storage tanks are challenging to deploy, and more difficult to extract and replace frequently due to radiological exposure and disposal constraints. Hence, electrodes that exhibit stable performance over long periods of immersion in these waste environments are desirable. The present study evaluates the stability of reference electrodes used in radioactive waste storage tanks over a much longer period than previously studied. Long-term tests on Ag/AgCl and Hg/HgO reference electrodes were performed in nonradioactive simulants formulated from wastes stored at the Hanford site. Electrode degradation, which was studied by various in situ and ex situ evaluation techniques, was correlated to changes in electrode fill chemistry from waste intrusion via the porous frit junction. An intentional contamination study was performed to better understand and predict contamination effects on electrode potential drift.

Creation of Cationic Polymeric Nanotrap Featuring High Anion Density and Exceptional Alkaline Stability for Highly Efficient Pertechnetate Removal from Nuclear Waste Streams.

There is an urgent need for highly efficient sorbents capable of selectively removing 99TcO4- from concentrated alkaline nuclear wastes, which has long been a significant challenge. In this study, we present the design and synthesis of a high-performance adsorbent, CPN-3 (CPN denotes cationic polymeric nanotrap), which achieves excellent 99TcO4- capture under strong alkaline conditions by incorporating branched alkyl chains on the N3 position of imidazolium units and optimizing the framework anion density within the pores of a cationic polymeric nanotrap. CPN-3 features exceptional stability in harsh alkaline and radioactive environments as well as exhibits fast kinetics, high adsorption capacity, and outstanding selectivity with full reusability and great potential for the cost-effective removal of 99TcO4-/ReO4- from contaminated water. Notably, CPN-3 marks a record-high adsorption capacity of 1052 mg/g for ReO4- after treatment with 1 M NaOH aqueous solutions for 24 h and demonstrates a rapid removal rate for 99TcO4- from simulated Hanford and Savannah River Site waste streams. The mechanisms for the superior alkaline stability and 99TcO4- capture performances of CPN-3 are investigated through combined experimental and computational studies. This work suggests an alternative perspective for designing functional materials to address nuclear waste management.

Gaussian process regression and conditional Karhunen-Loève models for data assimilation in inverse problems

We present a model inversion algorithm, CKLEMAP, for data assimilation and parameter estimation in partial differential equation models of physical systems with spatially heterogeneous parameter fields. These fields are approximated using low-dimensional conditional Karhunen-Loève expansions (CKLEs), which are constructed using Gaussian process regression (GPR) models of these fields trained on the parameters' measurements. We then assimilate measurements of the state of the system and compute the maximum a posteriori (MAP) estimate of the CKLE coefficients by solving a nonlinear least-squares problem. When solving this optimization problem, we efficiently compute the Jacobian of the vector objective by exploiting the sparsity structure of the linear system of equations associated with the forward solution of the physics problem.The CKLEMAP method provides better scalability compared to the standard MAP method. In the MAP method, the number of unknowns to be estimated is equal to the number of elements in the numerical forward model. On the other hand, in CKLEMAP, the number of unknowns (CKLE coefficients) is controlled by the smoothness of the parameter field and the number of measurements, and is generally much smaller than the number of discretization nodes, which leads to a significant reduction of computational cost with respect to the standard MAP method. To show this advantage in scalability, we apply CKLEMAP to estimate the transmissivity field in a two-dimensional steady-state subsurface flow model of the Hanford Site by assimilating synthetic measurements of transmissivity and hydraulic head. We find that the execution time of CKLEMAP scales nearly linearly as N1.33, where N is the number of discretization nodes, while the execution time of standard MAP scales as N2.91. The CKLEMAP method improved execution time without sacrificing accuracy when compared to the standard MAP method.

Interpretation of large‐scale, long‐term electrical geophysical monitoring guided by a process simulation

AbstractSurface electrical resistivity tomography (ERT) was used at a waste site to monitor vadose zone changes in electrical properties as a proxy for contaminant flux over a span of 17 years. The BC Cribs and Trenches (BCCT) site at the Hanford site contains 20 disposal trenches and six disposal cribs. Wastes include a large inventory of technetium‐99 and large masses of nitrate and uranium‐238. ERT data were collected along 41 profiles in 2005 to characterize regions of elevated bulk electrical conductivity (BEC) associated with past liquid waste discharges. Previous analyses performed on samples from four boreholes showed a high correlation between nitrate concentration and BEC. In 2022, ERT data were re‐collected along the same profiles and six additional profiles in an area not previously surveyed. Compared to background uncontaminated areas, BEC was higher in contaminated areas at the waste sites. Given the correlation between nitrate concentration and BEC previously found at this site, ERT images show the spatial distribution and relative ionic concentration of vadose zone contaminants at BCCT. Between 2005 and 2022, ERT difference images showed a decrease in BEC surrounding most waste sites, with exceptions where there were known anthropogenic surface changes. An evaluation of recharge‐driven nitrate migration using synthetic flow and transport simulations showed that downward migration causes a decrease in BEC from the decrease in ionic strength at the trailing end of the plume where contaminants migrated downward. From this, we interpret ERT difference images as showing the predominant regions of downward ion flux.

Effect of Adsorbed Carboxylates on the Dissolution of Boehmite Nanoplates in Highly Alkaline Solutions.

Understanding the dissolution of boehmite in highly alkaline solutions is important to processing complex nuclear waste stored at the Hanford (WA) and Savannah River (SC) sites in the United States. Here, we report the adsorption of model carboxylates on boehmite nanoplates in alkaline solutions and their effects on boehmite dissolution in 3 M NaOH at 80 °C. Although expectedly lower than at circumneutral pH, adsorption of oxalate occurred at pH 13, with adsorption decreasing linearly to 3 M NaOH. Classical molecular dynamics simulations suggest that the adsorption of oxalate dianions onto the boehmite surface under high pH can occur through either inner- or outer-sphere complexation mechanisms depending on adsorption sites. However, both adsorption models indicate relatively weak binding, with an energy preference of 1.26 to 2.10 kcal/mol. By preloading boehmite nanoplates with oxalate or acetate, we observed suppression of dissolution rates by 23 or 10%, respectively, compared to pure solids. Scanning electron microscopy and transmission electron microscopy characterizations revealed no detectable difference in the morphologic evolution of the dissolving boehmite materials. We conclude that preadsorbed carboxylates can persist on boehmite surfaces, decreasing the density of dissolution-active sites and thereby adding extrinsic controls on dissolution rates.

Draft genome sequences of two Pseudomonas strains isolated from 129I plumes at the Hanford Site.

Pseudomonas strains DVZ6 and DVZ24 were isolated from a sediment trap incubated in an 129I plume at the Hanford Site (Washington State, USA). Whole-genome sequencing of the strains revealed that both genomes are 5.77 Mb in size, with a G + C content of 64.75%.

Draft genome sequence of Enterobacter hormaechei DVZ29, an iodide-oxidizing bacterium isolated from the Hanford site.

Enterobacter hormaechei DVZ29 was isolated from a sediment trap incubated in an 129I plume at the Hanford Site (Washington State, USA). A whole genome sequencing of the strain resulted in 32 contigs and revealed that the genome is 4.90 Mb, with a G + C content of 55.61%.

Conditional Karhunen–Loève regression model with Basis Adaptation for high-dimensional problems: Uncertainty quantification and inverse modeling

We propose a methodology for improving the accuracy of surrogate models of the observable response of physical systems as a function of the systems’ spatially heterogeneous parameter fields, with applications to uncertainty quantification and parameter estimation in high-dimensional problems. Practitioners often formulate finite-dimensional representations of spatially heterogeneous parameter fields using truncated unconditional Karhunen–Loève expansions (KLEs) for a certain choice of unconditional covariance kernel and construct surrogate models of the observable response with respect to the KLE coefficients. When direct measurements of the parameter fields are available, we propose improving the accuracy of these surrogate models by representing the parameter fields via conditional Karhunen-Loève expansions (CKLEs). CKLEs are constructed by conditioning the covariance kernel of the unconditional expansion on the direct measurements of the parameter field via Gaussian process regression, and then truncating the corresponding KLE.We apply the proposed methodology to constructing surrogate models via the Basis Adaptation (BA) method of the stationary hydraulic head response, measured at spatially discrete observation locations, of a groundwater flow model of the Hanford Site, as a function of the 1000-dimensional representation of the model’s log-transmissivity field. We find that BA surrogate models of the hydraulic head based on CKLEs are more accurate than BA surrogate models based on unconditional expansions for forward uncertainty quantification tasks. Furthermore, we find that inverse estimates of the hydraulic transmissivity field computed using CKLE-based BA surrogate models are more accurate than those computed using unconditional BA surrogate models.

Quantifying Dense Multicomponent Slurries with In-Line ATR-FTIR and Raman Spectroscopies: A Hanford Case Study.

The multiphase nature of slurries can make them difficult to process and monitor in real time. For example, the nuclear waste slurries present at the Hanford site in Washington State are multicomponent, multiphase, and inhomogeneous. Current analytical techniques for analyzing radioactive waste at Hanford rely on laboratory results from an on-site analytical laboratory, which can delay processing speed and create exposure risks for workers. However, in-line probes can provide an alternative route to collect the necessary composition information. In the present work, Raman spectroscopy and attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy are tested on simulants of nuclear waste slurries containing up to 23.2 wt % solids. We observe ATR-FTIR spectroscopy to be effective in measuring the solution phase of the studied slurry systems (3.52% mean percent error), while Raman spectroscopy provides information about the suspended solids in the slurry system (18.21% mean percent error). In-line measurement of multicomponent solids typical of nuclear waste processing has been previously unreported. The composition of both the solution and solid phases is vital in ensuring stable glass formulation and effective disposal of nuclear waste at Hanford. Raman and ATR-FTIR spectroscopies can provide a safer and faster alternative for acquiring compositional information on nuclear waste slurries.

The evaluation of aluminum and iron metal oxide settling behaviors for Hanford insoluble solids waste preprocessing

AbstractThe Hanford site is currently one of the largest and most expensive cleanup sites for hazardous, radioactive waste. Over 20% of the waste found at the Hanford site is in the form of a high activity sludge. The insoluble solids in the sludge will need to be concentrated prior to vitrification in the high‐level waste (HLW) melter. This will minimize the amount of liquid that will be evaporated during the melting process and expedite the melter processing rate. One proposed option for concentrating the insoluble solids is gravity settling in the storage tanks. Metal oxide compounds containing aluminum and iron make up the majority of the insoluble solids in the sludge, therefore understanding the behavior of these compounds in various tank waste matrices can facilitate sludge pretreatment options. A study of non‐radioactive slurry solutions containing Al(OH)3 (gibbsite), AlO(OH) (boehmite), and Fe2O3 (iron (III) oxide) was conducted to determine the time dependent interface behavior and settling rates of these compounds. Variations in solids loading and sodium concentration were evaluated to represent waste processing conditions and the results of these settling studies were compared with prior tank waste settling tests. Information gathered from these studies can be used to inform future decisions on sludge treatment processes of the insoluble solids processed at the Hanford site.

Tracking Sensor Location by Video Analysis in Double-Shell Tank Inspections

Double-shell tanks (DSTs) are a critical part of the infrastructure for nuclear waste management at the U.S. Department of Energy’s Hanford site. They are expected to be used for the interim storage of partially liquid nuclear waste until 2050, which is the target date for completing the immobilization process for all Hanford nuclear waste. At that time, DSTs will have been used about 15 years beyond their original projected lifetime. Consequently, for the next approximately 30 years, Hanford DSTs will undergo periodic nondestructive evaluation (NDE) to ensure their integrity. One approach to perform NDE is to use ultrasonic data from a robot moving through air slots, originally designed for cooling, in the confined space between primary and secondary tanks. Interpreting ultrasonic sensor output requires knowing where measurements were taken with a precision of approximately one inch. Analyzing video acquired during inspection is one approach to tracking sensor location. The top edge of an air slot is easily detected due to the difference in color and texture between the primary tank bottom and the air slot walls. A line fit to this edge is used in a model to calculate the apparent width of the air slot in pixels at targets near the top edge that can be recognized in video images. The apparent width of the air slot at the chosen target in a later video frame determines how far the robot has moved between those frames. Algorithms have been developed that automate target selection and matching in later frames. Tests in a laboratory mockup demonstrated that the method tracks the location of the ultrasonic sensor with the required precision.