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At least 145 records · Page 8

Unveiling the effect of composition on nuclear waste immobilization glasses’ durability by nonparametric machine learning

Abstract Ensuring the long-term chemical durability of glasses is critical for nuclear waste immobilization operations. Durable glasses usually undergo qualification for disposal based on their response to standardized tests such as the product consistency test or the vapor hydration test (VHT). The VHT uses elevated temperature and water vapor to accelerate glass alteration and the formation of secondary phases. Understanding the relationship between glass composition and VHT response is of fundamental and practical interest. However, this relationship is complex, non-linear, and sometimes fairly variable, posing challenges in identifying the distinct effect of individual oxides on VHT response. Here, we leverage a dataset comprising 654 Hanford low-activity waste (LAW) glasses across a wide compositional envelope and employ various machine learning techniques to explore this relationship. We find that Gaussian process regression (GPR), a nonparametric regression method, yields the highest predictive accuracy. By utilizing the trained model, we discern the influence of each oxide on the glasses’ VHT response. Moreover, we discuss the trade-off between underfitting and overfitting for extrapolating the material performance in the context of sparse and heterogeneous datasets.

36 MATERIALS SCIENCE↗

Hanford Double Shell Waste Tank Corrosion Studies FY2020 (Final Report)

For fiscal year (FY) 2020, the Savannah River National Laboratory (SRNL) focused on three experimental tasks related to Hanford Double Shell Tank (DST) chemistry and integrity. The first task focused on understanding risk of corrosion due to formation of either continuous layers or discrete patches of deposits on the tanks’ inner sidewalls and bottoms. The second task studied vapor space corrosion (VSC) of the secondary liner using two commercially available vapor corrosion inhibitors (VCIs) at manufacturer recommended dosages. Finally, the third task investigated the long-term open circuit potential (OCP) drift for mill-scale coupons, coupons with polished surfaces, and partial mill-scale coupons that were exposed to tank waste simulants. Additional tests were performed to evaluate the OCP drift as a function of the quantity and composition of organic compounds added to the simulant. A test that was included in the matrix that established the new chemistry limits for tank corrosion, but was previously unreported, was presented and reviewed as well.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Chemical recycling of scrap composites

There are no well-developed technologies for recycling composite materials other than grinding to produce fillers. New approaches are needed to reclaim these valuable resources. Chemical or tertiary recycling, conversion of polymers into low molecular weight hydrocarbons for reuse as chemicals or fuels, is emerging as the most practical means for obtaining value from waste plastics and composites. Adherent Technologies is exploring a low-temperature catalytic process for recycling plastics and composites. Laboratory results show that all types of plastics, thermosets as well as thermoplastics, can be converted in high yields to valuable hydrocarbon products. This novel catalytic process runs at 200 C, conversion times are rapid, the process is closed and, thus, nonpolluting, and no highly toxic gas or liquid products have been observed so no negative environmental impact will result from its implementation. Tests on reclamation of composite materials show that epoxy, imide, and engineering thermoplastic matrices can be converted to low molecular weight hydrocarbons leaving behind the reinforcing fibers for reuse as composite reinforcements in secondary, lower-performance applications. Chemical recycling is also a means to dispose of sensitive or classified organic materials without incineration and provides a means to eliminate or reduce mixed hazardous wastes containing organic materials.

Allred, Ronald E.↗

Recycling waste-paper

Perhaps 80 percent of papermaking energy is expended in chemical pulping of vegetable cellulose, a natural polymer. Commercial supplies of wood, bagasse, cotton and flax are valued as renewable resources and bio-mass assets; however, few enterprises will salvage waste-paper and cardboard from their trash. A basic experiment in the Materials Lab uses simple equipment to make crude handsheets. Students learn to classify secondary fibers, identify contraries, and estimate earnings.

Widener, Edward L.↗

Overall assessment of alkali-silica reaction affected recycled concrete aggregate mixtures derived from construction and demolition waste

A large amount of research has been conducted on the reuse of construction and demolition waste (CDW) in concrete. Yet, CDW may display pre-existing damage which raises concerns on its use. In this work, coarse recycled concrete aggregate (RCA) is reclaimed from distinct members of an alkali-silica reaction (ASR) affected overpass. RCA mixtures incorporating 50 and 100% replacement are then manufactured and stored in conditions enabling further ASR development. Mechanical (Stiffness Damage Test- SDT) and microscopic (Damage Rating Index- DRI) analyses are conducted at a fixed “secondary” induced expansion. Results indicate that the overall damage of ASR-affected RCA mixtures is different from conventional concrete and depends upon the “past” RCA condition. Furthermore, the DRI can capture the “past” and “secondary” expansion while the SDT simply detects the “secondary” distress. Finally, an adapted DRI version is proposed to better evaluate and distinguish “past” and “secondary” damage in ASR-affected recycled concrete.

36 MATERIALS SCIENCE↗

Components Refurbishment and Chemical Analysis Facility, Hot Spot 1 SWMU #041 Year 3 Annual Performance Monitoring Report Kennedy Space Center, Florida

This Year 3 Annual Performance Monitoring Report (PMR) presents the operations, maintenance, and monitoring activities for the Hydraulic Containment System (HCS) Interim Measure (IM) at the Components Refurbishment and Chemical Analysis (CRCA) facility located at John F. Kennedy Space Center (KSC), Florida. The primary objective of the HCS is to attain hydraulic control of the dissolved-phase chlorinated volatile organic compound (CVOC) plume, with the secondary objective to reduce concentrations of CVOCs in the high-concentration plume to support transition to monitored natural attenuation (MNA). CRCA has been designated Solid Waste Management Unit 041 under the KSC Resource Conservation and Recovery Act Corrective Action Program. The timeframe for activities documented in this Year 3 PMR extends from September 2021 through October 2022. Baseline sampling activities were completed in June 2019, and full-scale startup of the HCS IM was completed in July-August 2019. The operational runtime of the HCS for the Year 3 reporting period was approximately 91%, with the majority of downtime attributed to system maintenance and repair. This is generally consistent with Year 1 and Year 2 runtimes of 85% and 92%, respectively. To help reduce downtime, an anti-scaling amendment, Redux 390, has been used to reduce scaling and help maintain system design parameters. Over nine million gallons of groundwater were treated during Year 3 of HCS operations, and concentrations of the site’s contaminants of concern (trans-1,2-dichloroethene and vinyl chloride) have been reduced by over 97%. This PMR describes the activities that were performed during Year 3 to operate and monitor the HCS IM, which includes three extraction wells, seven injection wells, and conveyance piping to a modular structure containing the control panel and an air stripper. Influent and effluent sampling results from the air stripper show that the system is operating as designed and is reducing concentrations of contaminants of concern to below detection limits. In addition to HCS operation, this PMR also discusses performance monitoring that has been implemented to assess progress of the HCS IM and overall plume conditions through scheduled groundwater (quarterly and semi-annual) and sub-slab soil gas (quarterly) sampling and analysis. Two ambient air samples were also collected on a quarterly basis in the vicinity of the modular structure and the paved driveway east of the Solvent Reclamation Area during routine operation and maintenance (O&M) activities to ensure safe breathing zone air quality for on-site personnel. All sub-slab soil gas and ambient air sampling conducted during the Year 3 operational period showed results below applicable regulatory air screening limits. Predictions made during the Year 2 groundwater model updates were in close correlation to post Year 3 plume conditions. Therefore, it can be assumed that the projected path remains valid for transition to MNA in one to two years of continuous HCS operation. The contents of this Year 3 PMR were presented during the February 2023 KSC Remediation Team meeting, where Team consensus was reached on several items including continued O&M of the HCS, and continued monitoring of groundwater, ambient air, and sub-slab soil gas. Replacement of MW0019 and VMP04 was also recommended, as well as additional direct-push technology sampling to further delineate the downgradient plume and confirm overall site-wide low-concentration plume boundaries. Sampling for per- and polyfluoroalkyl substances at CRCA is ongoing and will be submitted under separate cover.

K. Alex Murphy↗

Hanford Double Shell Waste Tank Corrosion Studies (Final Report FY2021)

For fiscal year (FY) 2021, the Savannah River National Laboratory (SRNL) focused on two experimental tasks related to Hanford Double Shell Tank (DST) chemistry and integrity. The first task focused on understanding risk of corrosion due to formation of either continuous layers or discrete patches of deposits on the tanks’ inner sidewalls and bottoms. The second task studied vapor space corrosion (VSC) inhibition of the secondary liner using vapor corrosion inhibitors (VCIs) at dosages less than the manufacturer recommended and a control test in which no VCIs were added.

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Closure of Regenerative Life Support Systems: Results of the Lunar-Mars Life Support Test Project

Future long duration human exploration missions away from Earth will require closed-loop regenerative life support systems to reduce launch mass, reduce dependency on resupply and increase the level of mission self sufficiency. Such systems may be based on the integration of biological and physiocochemical processes to produce potable water, breathable atmosphere and nutritious food from metabolic and other mission wastes. Over the period 1995 to 1998 a series of ground-based tests were conducted at the National Aeronautics and Space Administration, Johnson Space Center, to evaluate the performance of advanced closed-loop life support technologies with real human metabolic and hygiene loads. Named the Lunar-Mars Life Support Test Project (LMLSTP), four integrated human tests were conducted with increasing duration, complexity and closure. The first test, LMLSTP Phase I, was designed to demonstrate the ability of higher plants to revitalize cabin atmosphere. A single crew member spent 15 days within an atmospherically closed chamber containing 11.2 square meters of actively growing wheat. Atmospheric carbon dioxide and oxygen levels were maintained by control of the rate of photosynthesis through manipulation of light intensity or the availability of carbon dioxide and included integrated physicochemical systems. During the second and third tests, LMLSTP Phases II & IIa, four crew members spent 30 days and 60 days, respectively, in a larger sealed chamber. Advanced physicochemical life support hardware was used to regenerate the atmosphere and produce potable water from wastewater. Air revitalization was accomplished by using a molecular sieve and a Sabatier processor for carbon dioxide absorption and reduction, respectively, with oxygen generation performed by water hydrolysis. Production of potable water from wastewater included urine treatment (vapor compression distillation), primary treatment (ultrafiltration/reverse osmosis and multi-filtration) and post processing. For the Phase II test the water recovery rate ranged from 95 to 98%, depending on the processor. LMLSTP Phase III, the fourth test of the series, had a duration of 91 days and included four crew members. The test demonstrated an integration of physicochemical and biological technologies for air revitalization, water recovery and waste processing. Wheat supplemented the physicochemical air revitalization systems by providing approximately 25% of the oxygen required for the 4-person crew. The water recovery system included immobilized cell and trickling filter bioreactors for primary water treatment, reverse osmosis and air evaporation systems for secondary water treatment, followed by post processing. The 8 day initial supply of water was recycled through the chamber and crew 10 times over the course of the test. Grain from the wheat together with fresh lettuce from a small growth chamber within the crew chamber provided supplementation to the stored food system, but at a level less than 5% of the crew s caloric requirement. An incinerator was used to demonstrate mineralization of the crew s solid waste, with the combustion products (mainly carbon dioxide) returned to the wheat for conversion to oxygen.

Barta, Daniel↗

PFAS Removal by Ion Exchange Resins: Background and Knowledge Gaps with Respect to the Hanford Site

Per- and polyfluoroalkyl substances (PFAS) have been a rising concern for the past two decades, with the United States Department of Defense and Environmental Protection Agency investing millions of dollars in research into remediation and clean-up technologies. Due to the environmental persistence, toxicity, biological uptake, and ongoing changes in both federal and state regulatory space, understanding the fate and transport of PFAS compounds has been of growing concern to the US Department of Energy (DOE). The DOE’s Hanford Site is investigating historical use of PFAS and will be doing site characterization for PFAS. Thus, PFAS have not yet been identified as a contaminant concern in regulatory documents. Based on historical records that mention the discharge of aqueous film-forming foam containing PFAS and having on-site fire stations (a risk factor for PFAS contamination), it seems likely that environmental releases of PFAS may have occurred. Pump and treat (P&T) remediation is the selected remedy for multiple groundwater contaminant plumes at Hanford. These P&T systems use ion exchange (IX) as a component of aboveground treatment, with the specific resins depending on the target contaminants. There is potential that these IX resins may be able to remove PFAS from groundwater, but investigation is needed to understand affinity/selectivity and removal capacity given the groundwater composition and the operating conditions. This report provides background on PFAS uses and chemistry, then provides a review of IX resin applications for PFAS, identifying knowledge gaps. Recommendations are provided regarding research needed to address knowledge gaps and acquire information needed to propose IX as a future PFAS remediation technology at the Hanford Site, as well as other U.S. Department of Energy sites. Generally, PFAS compounds are fluorinated substances that contain at least one fully fluorinated methyl or methylene carbon – with a few noted exceptions, any chemical with at least a perfluorinated methyl group (–CF3) or a perfluorinated methylene group (–CF2–) is a PFAS. These chemical compounds are characterized as non-biodegradable, non-reactive, non-photolytic, and hydrolysis resistant. This makes them highly recalcitrant within the environment, however polyfluoroalkyl materials are less recalcitrant as the carbon chains contain C–H bonds which are more easily broken than carbon – fluorine (C–F) bonds. The backbone carbon structures are commonly punctuated with a head group, the most well-known of them are perfluorooctanesulfonic acid and perfluorooctanoic acid, which possess a sulfonate and a carboxylate group, respectively. IX resins are marketed for the removal of PFAS from water systems and industrial water, however, the mechanism of removal is not as well understood as for anion or cation removal. A better understanding of the mechanism of removal would enable the development of IX resins that have improved specificity for PFAS removal. Four knowledge gaps were identified: 1) the effect of dissolved ions on the IX resin PFAS removal effectiveness, 2) the effect of additional primary contaminants of concern (PCOCs) or secondary contaminants of concern (SCOCs) on the effectiveness of PFAS via IX resin, 3) the mechanisms of PFAS removal from water, and 4) practical solutions to IX resin regeneration and waste disposal.

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The effect of caustic soda treatment to recover rare earth elements from secondary feedstocks with low concentrations

Caustic soda (NaOH) treatment has enhanced rare earth element (REE) extraction from monazite. Here, this study examined the effectiveness of caustic soda for RE-phosphates with lower concentrations for extraction from coal overburden, an alternative feedstock derived from mining waste. Pourbaix (Eh-pH) diagrams were constructed for La, Ce, Nd, Eu, and Y-PO 4 -H 2 O systems to understand the thermodynamics of NaOH-facilitated acid leaching for low-concentration RE-phosphates and oxides and to elucidate the difference in recoveries among individual REEs. The Eh-pH diagrams indicated that low crystallinity is beneficial for extraction. Nd was thermodynamically most favorable for the extraction process among the five elements examined, and Y was the least promising. Experiments were conducted using three Pennsylvania coal overburden samples to validate the effect of caustic soda on rare earth leaching. The experimental results showed that for NaOH (6 M), a leaching time of 2 h at 125 °C was sufficient to obtain twice the recovery values compared to those without the NaOH treatment. After implementing the caustic soda treatment, a high total REE recovery (>60%), especially for Nd and Pr, could be achieved with diluted HCl and more environmentally friendlier citric acid. The results were similar for both coarse and fine particles. This novel approach is likely to improve the feasibility of REE extraction from coal-associated feedstock in a more environmentally benign manner.

42 ENGINEERING↗

Exploring Secondary Markets to Improve Circularity: A Comparative Case Study of Photovoltaics and Hard-Disk Drives

Each year renewable energy generation increases notably with solar panel installations, but these panels have a limited lifespan and will produce between 2 and 4 million metric tons of waste by 2040. Similarly, there are currently between 20 to 70 million hard-disk drives (HDDs) reaching end-of-life (EOL) annually. The circular economy (CE) strives to recycle and reuse materials that are rare and expensive to obtain, minimizing waste. However, studying the potential circularity of photovoltaics (PV) and HDDs requires various data, for instance, on the maturity of the secondhand markets. In this context, the objective of the present study is to identify the current state of secondhand PV and HDD markets. After conducting a literature review, an automated data collection process was set up for that purpose. The analysis of the literature and collected data assess the maturity of the secondhand PV modules and HDDs markets and highlight differences between them.

agent-based modelling↗

Strategy for the reduction of total integrated fluid logistics to the Space Station Freedom

The use of an integrated environmental control and life support system (ECLSS) and secondary propulsion system (SRS) on the Space Station Freedom (SSF) has many potential advantages. Through the metabolism of food, the crew on-board the station will produce carbon dioxide as a waste gas and an excess of water in the form of urine and condensate. The processing of these waste fluids by the ECLSS could produce quantities of oxygen that would eliminate the need for cryogenic oxygen resupply and hydrogen, carbon dioxide, and/or methane that could be used with the addition of a resistojet system to provide a constant low thrust for station. This additional thrust would represent significant savings in required hydrazine resupply.

Gould, Marston J.↗

Air augmented conventional rocket engines

An analytical study was conducted to assess and estimate the level of effectiveness of an ejector/rocket or rocket engine nozzle after-burning concept for enhancement of a conventional rocket engine. Performance enhancement and thrust augmentation of an ejector/rocket system were evaluated for a National (or Advanced) Launch System (LNS or ALS) type engine, namely the Space Transportation Main Engine (STME), and its effects on the overall vehicle/propulsion system as payload weight, gross lift-off weight, and propellant weight. The focus was on using a fixed geometry ejector and utilizing the otherwise wasted exhaust excess fuel of rocket engines and burning it with injested atmospheric air to produce additional thrust. Limited analyses were also performed to determine the effect of burning additional injected fuel with the secondary air on thrust augmentation.

Fahahngi, Shahram↗

Potential Application of Anaerobic Extremophiles for Hydrogen Production

During substrate fermentation many anaerobes produce the hydrogen as a waste product, which often regulates the growth of the cultures as an inhibitor. In nature the hydrogen is usually removed from the ecosystem due to its physical properties or by consumption of hydrogen by secondary anaerobes, which sometimes behave as competitors for electron donors as is seen in the classical example in anaerobic microbial communities via the interaction between methanogens and sulfate- or sulfur- reducers. It was demonstrated previously on mixed cultures of anaerobes at neutral pH that bacterial hydrogen production could provide an alternative energy source. But at neutral pH the original cultures can easily be contaminated by methanogens, a most unpleasant side effect of these conditions is the development of pathogenic bacteria. In both cases the rate of hydrogen production was dramatically decreased since some part of the hydrogen was transformed to methane, and the cultivation of human pathogens on a global scale is very dangerous. In our laboratory, experiments with obligately alkaliphilic bacteria that excrete hydrogen as the end metabolic product were performed at different temperature regimes. Mesophilic and moderately thermophilic bacterial cultures have been studied and compared for the most effective hydrogen production. For high-mineralized media with pH 9.5-10.0 not many methanogens are known to exist. Furthermore, the development of pathogenic contaminant microorganisms is virtually impossible: carbonate-saturated solutions are used as antiseptics in medicine. Therefore the cultivation of alkaliphilic hydrogen producing bacteria could be considered as most safe process for global Scale industry in future. Here we present experimental data on the rates of hydrogen productivity for mesophilic, alkaliphilic, obligately anaerobic bacterium Spirocheta americana ASpG1 and moderately thermophilic, alkaliphilic, facultative anaerobe Anoxybacillus pushchinoensis K1 and discuss the potential implications for alternative energy sources.

Pikuta, Elena V.↗

In situ liquid SEM imaging analysis revealing particle dispersity in aqueous solutions

A quantitative description on dispersity of boehmite (γ-AlOOH) particles, a key component for waste slurry at Hanford sites, can provide useful knowledge for understanding various physicochemical nature of the waste. In this work, in situ liquid scanning electron microscopy (SEM) was used to evaluate the dispersity of particles in aqueous conditions using a microfluidic sample holder, System for Analysis at Liquid Vacuum Interface (SALVI). Secondary electron (SE) images and image analyses were performed to determine particle centroid locations and the distance to the nearest neighbour particle centroid, providing reliable rescaled interparticle distances as a function of ionic strength in acidic and basic conditions. Our finding of the particle dispersity is consistent with physical insights from corresponding particle interactions under physicochemical conditions, demonstrating delicate changes in dispersity of boehmite particles based on novel in situ liquid SEM imaging and analysis.

47 OTHER INSTRUMENTATION↗

Struvite crystallization

The present invention provides a method and apparatus for removing phosphorus from phosphorus containing waste. In one embodiment, the method is preferably carried out by contacting the phosphorus containing waste with a non-cellular membrane and precipitating phosphorus from the waste as struvite. Another aspect of the invention includes a method of removing phosphorus from phosphorus containing sewage comprising filtrates and biosolids. The removal of phosphorus as struvite occurs in two stages as primary and secondary removal. In the primary removal process, the sewage from a dewatering unit is contacted with a first polymeric membrane reactor and the phosphorus is removed as primary struvite. Subsequently Mg is added so as promote struvite formation and the secondary removal process of struvite. In the secondary removal process, the sewage from GBT Filtrate well or Centrifuge Liquor well is contacted with a second monomolecular membrane and the phosphorus is removed as secondary struvite.

Barak, Phillip W.↗

Rapid AI-based Dissection of Ashes using Raman and XRF Spectroscopy (RADAR-X)

Waste-to-energy (WTE) facilities incinerate ~35 million tons of municipal solid waste annually in the United States. The incineration process reduces the mass and the volume of the waste fraction by over 75 and 95%, respectively. The fraction left after incineration remains as ash residues and is referred to as WTE ash, compromising of bottom and fly ash. In the United States, ~10 million tons of WTE ashes are generated annually and predominantly landfilled because of the lack of secondary end-use pathways. This incurs a significant financial burden (landfilling costs) on U.S. WTE facilities and also results in the loss of materials to the landfill. The primary objective of this research is to understand better the elemental and mineralogical composition of WTE ashes from diverse origins and find composition dependent upcycling pathways for diverting these ashes from landfills. This primary objective was addressed through three research tasks –(Task I) An AI-led Multi-Modal Approach for Compositional Analysis, (Task II) Developing a Dissolution-Based Test for Real Time Analysis, and (Task III) Establishing composition-dependent end uses. The chemical composition of WTE ash is dependent on two factors, i.e., the input waste composition and the operational parameters of a WTE facility (combustion conditions). Amongst these two factors, the input waste composition will likely show spatial and temporal variation. As a result, the chemical composition of WTE ash will also fluctuate. To understand the spatial and temporal variation in WTE ash composition, in Task I, we collected 128 ash samples (62 bottom ash and 66 fly ash samples) from 11 WTE facilities located in 11 U.S. states and characterized them via X-ray Fluorescence, powder X-ray Diffraction, and Raman Spectroscopy. The findings from this extensive characterization work indicated that the key elements in WTE fly ashes are Ca, Cl (greater than 10 wt. %), Si, S, K, Zn ( between 1 and 10 wt. %), Mg, Al, P, Ti, Fe, Cu, Br, and Pb (between 0.1 and 1 wt. %). Similarly, the key elements in WTE bottom ash fraction finer than 45μm are Ca (greater than 10 wt. %), Mg, Al, Si, S, Cl, K, Ti, Fe, Zn (between 1 and 10 wt. %), P, V, Cr, Mn, Cu, Br, and Pb (between 0.1 and 1 wt. %). Here, we note that the dominant fraction of WTE bottom ash is the coarse fraction. The coarse WTE bottom ash fraction (rich in silicon) was not characterized in this study because of excessive grinding requirements and their unsuitability as a supplementary cementitious material due to their coarse nature. The elements in WTE bottom ashes are present as calcite, anhydrite, vaterite, hydroxyapatite, quartz, bassanite, gehlenite, akermanite, hydrocalumite, and portlandite. Similarly, the mineralogical species present in WTE fly ashes are calcium chloride hydroxide, halite, calcite, anhydrite, sylvite, hydrocalumite, vaterite, hannebachite, quartz, and bassanite. Temporal variation in ash composition may also result in significant fluctuations in chemical compositions. Therefore, a WTE facility may need to monitor the ash composition (elemental and mineralogical composition) in real time. In Task I, we evaluated the possibility of using a portable X-ray fluorescence (XRF) spectrometer to monitor the elemental composition in real-time. Specifically, we collected XRF data on identical specimens via a portable XRF spectrometer (low-end) and a lab-based benchtop XRF spectrometer (high-end). The collected data was used to train an A.I. algorithm (portable XRF data as an input and benchtop XRF data as an output) to predict accurate elemental composition using portable XRF data. Finally, we developed a 2-minute photobleaching protocol to monitor the mineralogical characteristics of WTE ashes via Raman spectroscopy. Overall, the activities in Task I improved our understanding of ash composition and developed techniques to monitor elemental and mineralogical composition in near real-time. Based on the findings of Task I, we find that WTE ashes exhibit wide variability in mineralogy. For ICP-based elemental analysis, all the mineralogical species in WTE ashes must be brought into solution. This is traditionally accomplished with acid digestion using a combination of multiple acids. However, acid digestion with multiple acids is time-consuming and often fails to ensure complete digestion of the ash matrix. To address this limitation, in Task II, we developed an alkali-fusion-based digestion protocol using a combination of lithium tetraborate, lithium metaborate, and their combinations as possible alkali fluxes for digesting WTE ashes entirely and rapidly. The validity of the developed method was evaluated on two standard ash specimens, i.e., SRM 1633c coal fly ash and BCR-176R incineration fly ash specimen. The findings suggest that the developed protocol can ensure complete digestion of elements such as Al, Ba, Ca, Cr, Cu, Mg, Mn, P, Sr, V, Zn, Be, K, and rare earth elements. The recent changes in the energy market towards renewables and increased metal recycling have resulted in reduced supplies of supplementary cementitious materials (coal fly ash and slag). Therefore, in Task III, we evaluated the possibility of employing WTE ashes as SCMs. As the chemical composition of WTE ashes varies temporally (on an hourly basis), there was also a need to develop tests that can evaluate the suitability of material to act as supplementary cementitious material rapidly, i.e., in a few minutes. Therefore, in Task II, we also developed a rapid test to assess the suitability of a material to act as an SCM in 5 minutes. This represents a significant advance over the state-of-the-art R 3 test, which takes ~144 hours. This test was initially validated on amorphous aluminosilicates, such as calcined clays, and could be extended to evaluate other industrial by-products, such as WTE ashes. In Task III, we evaluated the possibility of employing WTE ashes for two applications, i.e., as an SCM and a lime substitute for clay stabilization. The findings from Task I indicated that WTE ashes are enriched in chlorine and, therefore, cannot be used directly as an SCM due to corrosion-related risks and altered hydration kinetics. Accordingly, we developed an ash treatment protocol to reduce the solubility of chlorine-containing species in WTE ashes. The developed treatment protocol also immobilized lead in certain mineral forms. As a result of the treatment, WTE ashes can be used as SCMs without any corrosion or heavy metal leaching concerns. The second application examined in this study was clay stabilization. WTE ashes are calcium-rich and can be an adequate lime replacement for clay stabilization. Our findings reveal that the sum of the concentrations of Ca(OH) 2 and CaClOH controls the clay stabilization capability of WTE ashes. In summary, in this work, we evaluated the elemental and mineralogical characteristics of U.S. WTE ashes from diverse origins and developed tests to evaluate the chemical characteristics of these ashes in real time through a portable XRF and a benchtop Raman spectrometer. Based on the chemical characteristics of these ashes, we developed an ash treatment process to enable the use of WTE ashes as an SCM and also evaluated the possibility of employing these ashes for clay stabilization. Overall, the findings from this work enables the diversion of WTE ashes from landfills for multiple end-uses, i.e., as an SCM or a lime substitute for clay stabilization.

36 MATERIALS SCIENCE↗

Hanford Double Shell Waste Tank Corrosion Studies (Final Report FY2019)

During fiscal year (FY) 2019, the Savannah River National Laboratory (SRNL) focused on four primary tasks for Hanford Double Shell Tanks (DSTs) corrosion studies. The first task, New Limits, was a continuation from the electrochemical work started in FY16, to expand electrochemical testing to elevated temperatures and elevated hydroxide concentrations and evaluate how these factors will influence pitting corrosion. Using the pitting factor (PF) equation, these new conditions were validated to provide a conservative estimate for the susceptibility of pitting corrosion on legacy carbon steel. The second task, Secondary Liner Corrosion, focused on Vapor Space Corrosion (VSC) and immersion testing studies using two commercially available vapor corrosion inhibitors (VCIs). For this FY, the VCI strategy was applied mid-experiment to determine performance on weathered coupons. The third task, Long-Term Open Circuit Potential (OCP) Drift, was performed using simplified simulated chemistries to evaluate change in pitting corrosion risk due to evolution of corrosion potential for mill-scale and freshly polished 600-grit surfaces. Finally, the fourth task, Microbiologically-Influenced Corrosion (MIC) studies, was focused on the study of leak detection pit (LDP) water sent from the Hanford tank farm for determination of bacteria that can be conducive to corrosion using commercially available kits: BART TM and MICkit® 5. In addition, this FY, a secondary task was added which was a continuation of the study of the Quartz-enhanced Photoacoustic Spectroscopy (QEPAS) system. Work was started but was ultimately not pursued. A summary of each task performed is presented below.

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