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At least 343 records · Page 19
All sourcesNASA NTRSDOE OSTI
DOE OSTI2017

Liquid secondary waste: Waste form formulation and qualification

The Hanford Site Effluent Treatment Facility (ETF) currently treats aqueous waste streams generated during site cleanup activities. When the Hanford Tank Waste Treatment and Immobilization Plant (WTP) begins operations, including Direct Feed Low Activity Waste (DFLAW) vitrification, a liquid secondary waste (LSW) stream from the WTP will need to be treated. The volume of effluent for treatment at the ETF will increase significantly. The powdered salt waste form produced by the ETF will be replaced by a stabilized solidified waste form for disposal in Hanford’s Integrated Disposal Facility (IDF). Washington River Protection Solutions is implementing a Secondary Liquid Waste Immobilization Technology Development Plan to address the technology needs for a waste form and solidification process to treat the increased volume of waste planned for disposal at the IDF. Waste form testing to support this plan is composed of work in the near term to provide data as input to a performance assessment (PA) for Hanford’s IDF. In 2015, three Hanford Liquid Secondary Waste simulants were developed based on existing and projected waste streams. Using these waste simulants, fourteen mixes of Hanford Liquid Secondary Waste were prepared and tested varying the waste simulant, the water-to-dry materials ratio, and the dry materials blend composition.1 In FY16, testing was performed using a simulant of the EMF process condensate blended with the caustic scrubber—from the Low Activity Waste (LAW) melter—, processed through the ETF. The initial EMF-16 simulant will be based on modeling efforts performed to determine the mass balance of the ETF for the DFLAW.2 The compressive strength of all of the mixes exceeded the target of 3.4 MPa (500 psi) to meet the requirements identified as potential IDF Waste Acceptance Criteria in Table 1 of the Secondary Liquid Waste Immobilization Technology Development Plan.3 The hydraulic properties of the waste forms tested (hydraulic conductivity and water characteristic curves) were comparable to the properties measured on the Savannah River Site (SRS) Saltstone waste form. Future testing should include efforts to first; 1) determine the rate and amount of ammonia released during each unit operation of the treatment process to determine if additional ammonia management is required, then; 2) reduce the ammonia content of the ETF concentrated brine prior to solidification, making the waste more amenable to grouting, or 3) manage the release of ammonia during production and ongoing release during storage of the waste form, or 4) develop a lower pH process/waste form thereby precluding ammonia release.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2021

Immobilization of cesium and iodine into Cs 3 Bi 2 I 9 perovskite-silica composites and core-shell waste forms with high waste loadings and chemical durability

Cs$_3$Bi$_2$I$_9$, a defect perovskite derivative, is a potential host phase to immobilize iodine and cesium with high waste loadings. In this work, two strategies were explored to form Cs$_3$Bi$_2$I$_9$-silica composites and a core-shell structure in order to improve chemical durability of waste form materials meanwhile maintaining high waste loadings. Cs$_3$Bi$_2$I$_9$ loadings as high as 70 wt.% were incorporated into a silica matrix to form silica-ceramic composites, and 20 wt.% Cs$_3$Bi$_2$I$_9$ was encapsulated into silica to form a core–shell structure by low temperature spark plasma sintering. Chemical durability of the composite and core-shell waste forms was evaluated by semi-dynamic leaching experiments, and Cs and I were incongruently released from waste form matrices. A BiOI alteration layer formed, acting as a passivation layer to reduce the release of radionuclides. The long-term iodine release rate was low (30 mg m$^{-2}$ day$^{-1}$) for the 70 wt.%Cs$_3$Bi$_2$I$_9$–silica composite leached in deionized water at 90 °C, which can be further reduced to 5 × 10$^{-3}$ mg m$^{-2}$ day$^{-1}$ for the 20 wt.% core-shell structure. This work highlights a robust way to immobilize the highly mobile radionuclides with high waste loadings through encapsulation into durable matrices and a surface passivating mechanism that can greatly reduce the elemental transport from waste form materials and significantly enhance their chemical durability.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Ripple Effects: Bed Form Morphodynamics Cascading Into Hyporheic Zone Biogeochemistry

The water quality and ecosystem health of river corridors depend on the biogeochemical processes occurring in the hyporheic zones (HZs) of the beds and banks of rivers. HZs in riverbeds often form because of bed forms. Despite widespread and persistent variation in river flow, how the discharge- and grain size-dependent geometry of bed forms and how bed form migration collectively and systematically affects hyporheic exchange flux, solute transport, and biogeochemical reaction rates are unknown. As such, we investigated these linked processes through morphodynamically consistent multiphysics numerical simulation experiments. Several realistic ripple geometries based on bed form stability criteria using mean river flow velocity and median sediment grain size were designed. Ripple migration rates were estimated based primarily on the river velocity. The ripple geometries and migration rates were used to drive hyporheic flow and reactive transport models which quantified HZ nitrogen transformation. Results from fixed bed form simulations were compared with matching migrating bed form scenarios. We found that the turnover exchange due to ripple migration has a large impact on reactant supply and reaction rates. The nitrate removal efficiency increased asymptotically with Damköhler number for both mobile and immobile ripples, but the immobile ripple always had a higher nitrate removal efficiency. Since moving ripples remove less nitrogen, and may even be net nitrifying at times, consideration for bed form morphodynamics may therefore lead to reduction of model-based estimates of denitrification. The connection between nitrate removal efficiency and Damköhler number can be integrated into frameworks for quantifying transient, network-scale, HZ nitrate dynamics.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2020

Unified model of nucleon elastic form factors and implications for neutrino-oscillation experiments

Precise knowledge of the nucleon’s axial-current form factors is crucial for modeling GeV-scale neutrino-nucleus interactions. Unfortunately, the axial form factor remains insufficiently constrained to meet the precision requirements of upcoming long-baseline neutrino-oscillation experiments. This work studies the nucleon’s axial and vector form factors using the light-front approach to build a quark-diquark model of the nucleon with an explicit pion cloud. The light-front wave functions in both the quark and pion-baryon Fock spaces are first calibrated to existing experimental information on the nucleon’s electromagnetic form factors and then used to predict the axial form factor. The resulting squared charge radius of the axial pseudovector form factor is predicted to be $r$$^{2}_{A}$ = 0.29 ± 0.03 fm 2 , where the small error accounts for the model’s parametric uncertainty. We use our form factor results to explore the (quasi)elastic scattering of neutrinos by (nuclei)nucleons, with the result that the widely implemented dipole ansatz is an inadequate approximation of the full form factor for modeling both processes. Here, the approximation leads to a 5%–10% overestimation of the total cross section, depending on the (anti)neutrino energy. We project overestimations of similar size in the flux-averaged cross sections for the upcoming DUNE long-baseline neutrino-oscillation experiment.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2011

Evolved QCD predictions for the meson-photon transition form factors: beyond the semiclassical AdS/QCD approximation

The QCD evolution of the pion distribution amplitude (DA) {phi}{sub {pi}} (x, Q{sup 2}) is computed for several commonly used models. Our analysis includes the nonperturbative form predicted by lightfront holographic QCD, thus combining the nonperturbative bound state dynamics of the pion with the perturbative ERBL evolution of the pion distribution amplitude. We calculate the meson-photon transition form factors for the {pi}{sup 0}, {eta} and {eta}' using the hard-scattering formalism. We point out that a widely-used approximation of replacing {phi} (x; (1 - x)Q) with {phi} (x;Q) in the calculations will unjustifiably reduce the predictions for the meson-photon transition form factors. It is found that the four models of the pion DA discussed give very different predictions for the Q{sup 2} dependence of the meson-photon transition form factors in the region of Q{sup 2} > 30 GeV{sup 2}. More accurate measurements of these transition form factors at the large Q{sup 2} region will be able to distinguish the four models of the pion DA. The rapid growth of the large Q{sup 2} data for the pion-photon transition form factor reported by the BABAR Collaboration is difficult to explain within the current framework of QCD. If the BABAR data for the meson-photon transition form factor for the {pi}{sup 0} is confirmed, it could indicate physics beyond-the-standard model, such as a weakly-coupled elementary C = + axial vector or pseudoscalar z{sup 0} in the few GeV domain, an elementary field which would provide the coupling {gamma}{sup *}{gamma} {yields} z{sup 0} {yields} {pi}{sup 0} at leading twist. Our analysis thus indicates the importance of additional measurements of the pion-photon transition form factor at large Q{sup 2}.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2025

Forming Limits of Thin Ferritic Stainless Steel for Fuel Cell Application

To lower the cost of fuel cell bipolar plate (BPP), less expensive ferritic stainless steel (FSS) BPP substrate materials are investigated. A series of tensile tests and multistage microchannel-forming tests were conducted on 85-µm-thick ferritic stainless steel foils, 439L, 444, and Chromeshield® 22, to understand the effect of the forming temperatures, tooling geometry, and processes on their formability. Three microchannel-forming processes were conducted, which are 1-Hit (single-stage forming), 2-Hit (two-stage forming) with 50% preform, and 2-Hit with 80% preform. FLC o s at various microchannel-forming conditions were obtained to address the formability of the ferritic stainless steel foils under plane strain conditions. It has been found that the larger the microchannel radius, the better the formability, two-stage forming is superior to the single-stage process, and a larger draw percentage in preform (stage I) leads to a higher FLC o or better formability. It has also been found from tensile tests that the thermal effect (higher temperature) has a negative impact on the failure strains. A similar phenomenon was also observed through channel-forming tests conducted at room temperature, 100 °C, and 200 °C.

08 HYDROGEN↗
DOE OSTI2017

Performance of a Steel/Oxide Composite Waste Form for Combined Waste Steams from Advanced Electrochemical Processes

The results of electrochemical corrosion tests and modeling activities performed collaboratively by researchers at the University of Illinois at Chicago and Argonne National Laboratory as part of workpackage NU-13-IL-UIC-0203-02 are summarized herein. The overall objective of the project was to develop and demonstrate testing and modeling approaches that could be used to evaluate the use of composite alloy/ceramic materials as high-level durable waste forms. Several prototypical composite waste form materials were made from stainless steels representing fuel cladding, reagent metals representing metallic fuel waste streams, and reagent oxides representing oxide fuel waste streams to study the microstructures and corrosion behaviors of the oxide and alloy phases. Microelectrodes fabricated from small specimens of the composite materials were used in a series of electrochemical tests to assess the corrosion behaviors of the constituent phases and phase boundaries in an aggressive acid brine solution at various imposed surface potentials. The microstructures were characterized in detail before and after the electrochemical tests to relate the electrochemical responses to changes in both the electrode surface and the solution composition. The results of microscopic, electrochemical, and solution analyses were used to develop equivalent circuit and physical models representing the measured corrosion behaviors of the different materials pertinent to long-term corrosion behavior. This report provides details regarding (1) the production of the composite materials, (2) the protocol for the electrochemical measurements and interpretations of the responses of multi-phase alloy and oxide composites, (3) relating corrosion behaviors to microstructures of multi-phase alloys based on 316L stainless steel and HT9 (410 stainless steel was used as a substitute) with added Mo, Ni, and/or Mn, and (4) modeling the corrosion behaviors and rates of several alloy/oxide composite materials made with added lanthanide and uranium oxides. These analyses show the corrosion behaviors of the alloy/ceramic composite materials are very similar to the corrosion behaviors of multi-phase alloy waste forms, and that the presence of oxide inclusions does not impact the corrosion behaviors of the alloy phases. Mixing with metallic waste streams is beneficial to lanthanide and uranium oxides in that they react with Zr in the fuel waste to form highly durable zirconates. The measured corrosion behaviors suggest properly formulated composite materials would be suitable waste forms for combined metallic and oxide waste streams generated during electrometallurgical reprocessing of spent nuclear fuel. Electrochemical methods are suitable for evaluating the durability and modeling long-term behavior of composite waste forms: the degradation model developed for metallic waste forms can be applied to the alloy phases formed in the composite and an affinity-based mineral dissolution model can be applied to the ceramic phases.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2017

Low Temperature Waste Form for Supplemental Immobilization of Hanford Low Activity Waste - 17485

The Hanford site has approximately 56 million gallons of radioactive waste stored in 177 underground storage tanks. The Hanford Waste Treatment and Immobilization Plant (WTP) is being constructed to treat the waste but will only have sufficient capacity to treat about one-third of the Low Activity Waste (LAW) portion within the anticipated time-frame for completing the waste treatment mission. The LAW vitrification facility will need to be supplemented with additional LAW vitrification capacity or an alternate LAW immobilization technology. The LAW immobilization technologies considered must be capable of treating approximately 65% of Hanford's LAW and will be evaluated with respect to facilities required, quantity of final waste forms and secondary wastes produced, waste form performance data, technical viability, and life cycle cost and schedule estimates. A low temperature (i.e. non-thermal) waste form and treatment process is being evaluated to provide the additional LAW immobilization capacity. Low temperature, cementitious waste forms have been evaluated previously for immobilizing Hanford tank waste but were not further developed for various reasons. Over the past few years the Hanford Tank Operations Contractor has conducted a technology development program to evaluate a low temperature waste form for immobilization of Hanford LAW including formulation development and testing with a range of simulant compositions spiked with radioactive and hazardous contaminants of concern (COCs). The objectives of this program include; developing a low temperature waste form formulation that is robust with respect to both waste form performance and processing properties over a range of LAW compositions, demonstrating waste form performance with real waste, and conducting Engineering Scale testing to advance the technical maturity of the low temperature immobilization process. The purpose of this paper is to report progress toward these objectives, in particular testing with real waste including additives to enhance technetium and iodine retention. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2019

Development of Polymer Waste Form for Spent Ion-Exchange Resins

A large amount of radioactive waste streams has been treated by ion-exchange resins at most of nuclear facilities for many years. These activities leave radionuclides as well as chemical contaminants on the spent resins, and the spent resins are considered as low- and intermediate-level radioactive waste. Spent ion-exchange resins require special immobilization treatment to meet the waste acceptance criteria for disposal. Immobilization of spent ion-exchange resins can be processed by mixing or incorporating them with suitable solidifying materials, such as cement, bitumen, organic polymers, and other materials or a combination of them. The selection of immobilization options for spent ion-exchange resins must consider their physical, chemical, and radiological characteristics. In this study, direct immobilization method was used to solidify the spent ion-exchange resins using organic polymer for improving the waste content. The objective of this study is to test the immobilization of spent ion-exchange resins using polymer waste form and enhance the solidified waste content. The specific objective of this study was to develop polymer waste form to solidify spent ion-exchange resins. Leaching (ANSI/ANS 16.1) and compressive strength tests were performed to meet the acceptance criteria of waste form for disposal. Ion-exchange resin has been solidified physically and chemically stable in the polymer waste form. The leaching test (ANSI/ANS16.1) for two polymer waste form specimens were conducted. The leachability indexes of sample A and B showed to meet the acceptance criteria for disposal. The compressive strength tested showed higher values in polymer waste form prepared with ion exchange resin compared to CoCl{sub 2} polymer form (sample B). Although spent resin was successively solidified in polymer matrix, the future experiment will develop a polymer waste form as a pre-treatment of spent resin for size reduction using a ball milling (500 RPM, 280 min)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2023

Extending the thermodynamic form factor bootstrap program: multiple particle-hole excitations, crossing symmetry, and reparameterization invariance

In this study, we further the thermodynamic bootstrap program which involves a set of recently developed ideas used to determine thermodynamic form factors of local operators in integrable quantum field theories. These form factors are essential building blocks for dynamic correlation functions at finite temperatures or non-equilibrium stationary states. In this work we extend this program in three ways. Firstly, we demonstrate that the conjectured annihilation pole axiom is valid in the low energy particle-hole excitations. Secondly, we introduce a crossing relation, which establishes a connection between form factors with different excitation content. Typically, the crossing relation is a consequence of Lorentz invariance, but due to the finite energy density of the considered states, Lorentz invariance is broken. Nonetheless a crossing relation involving excitations with both particles and holes can established using the finite volume representation of the thermodynamic form factors. Finally, we demonstrate that the thermodynamic form factors satisfy a reparameterization invariance, an invariance which encompasses crossing. Reparameterization invariance exploits the fact that the details of the representation of the thermodynamic state are unimportant. In the course of developing these results, we demonstrate the internal consistency of the thermodynamic form factor bootstrap program in a number of ways. Finally, we provide explicit computations of form factors of conserved charges and densities with crossed excitations and show our results can be used to infer information about thermodynamic form factors in the Lieb-Liniger model.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2017

Positive geometries and canonical forms

Recent years have seen a surprising connection between the physics of scattering amplitudes and a class of mathematical objects — the positive Grassmannian, positive loop Grassmannians, tree and loop Amplituhedra — which have been loosely referred to as “positive geometries”. The connection between the geometry and physics is provided by a unique differential form canonically determined by the property of having logarithmic singularities (only) on all the boundaries of the space, with residues on each boundary given by the canonical form on that boundary. The structures seen in the physical setting of the Amplituhedron are both rigid and rich enough to motivate an investigation of the notions of “positive geometries” and their associated “canonical forms” as objects of study in their own right, in a more general mathematical setting. In this paper we take the first steps in this direction. We begin by giving a precise definition of positive geometries and canonical forms, and introduce two general methods for finding forms for more complicated positive geometries from simpler ones — via “triangulation” on the one hand, and “push-forward” maps between geometries on the other. We present numerous examples of positive geometries in projective spaces, Grassmannians, and toric, cluster and flag varieties, both for the simplest “simplex-like” geometries and the richer “polytope-like” ones. We also illustrate a number of strategies for computing canonical forms for large classes of positive geometries, ranging from a direct determination exploiting knowledge of zeros and poles, to the use of the general triangulation and push-forward methods, to the representation of the form as volume integrals over dual geometries and contour integrals over auxiliary spaces. These methods yield interesting representations for the canonical forms of wide classes of positive geometries, ranging from the simplest Amplituhedra to new expressions for the volume of arbitrary convex polytopes.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2017

Processing of High-Entropy AlCoCr{sub 0.75}Cu{sub 0.5}FeNi Alloy by Spray Forming

Compositionally complex AlCoCrCuFeNi alloy system is one of the extensively studied high-entropy alloys (HEA). Most of these studies have been carried out on as-cast materials that witness slow cooling rate during solidification. In the present investigation, HEA based on AlCoCrCuFeNi system was processed employing spray forming so as to realize its inherent rapid solidification effect and unique microstructural evolution mechanism. The spray formed as well as the as-cast alloys were compared in terms of their microstructural features, phase constitution and hardness. These microstructural features were also compared with that of the overspray powders (< 250 µm) obtained as a by-product of spray forming. Both the as-cast and spray formed alloys showed a mixture of mainly two phases, i.e., face-centered and body-centered cubic (BCC) phases, in contrast to a single BCC phase in overspray powders. However, the spray formed alloy revealed unidentified phases, as against the as-cast material, which disappeared after heat treatment at 1473 K for 3 h. The grain size of the as-cast alloy was around 600-1000 μm compared to a highly refined grain size of 25-30 μm in the as-spray formed alloy. It was found that the hardness of the regions dominated by the constituent phases as well as the bulk of the spray formed material was higher than that of the as-cast alloy. The results validate the efficacy of the process in achieving drastic refinement in grain size, in a single step of large-scale spray forming. The characteristic microstructural features and the phase constitutions have been discussed in light of the prevailing mechanisms of structural evolution and possible solidification phenomena during spray atomization and deposition. This study gives a new direction in processing of these alloys and understanding their solidification behavior under the conditions of layer-by-layer deposition of semi-solid/liquid droplets.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Crystallization of Long-Spaced Precision Polyacetals I: Melting and Recrystallization of Rapidly Formed Crystallites

Rapidly melt-crystallized polyethylenes with acetal groups (-O-CH 2 -O-) precisely spaced by 12, 18, 19, or 23 backbone carbons exhibit two reorganizations and three melting endotherms on heating at relatively low heating rates. Real-time WAXD experiments further confirm that these transitions are associated with reorganization to a different crystalline structure. Here, the DSC endotherms are associated with melting of the initially formed disordered phase, followed by melting of Form I and by melting of Form II crystals with increasing temperature. In parallel with these structural changes, the long spacing undergoes a discrete step increase at the polymorphic transitions. Upon the transition from disordered to Form I crystals, the core crystal thickness increases by one repeating unit, whereas the crystal thickness remains basically unchanged during the transition from Form I to Form II crystallites. The effect of even vs. odd CH2 spacer on the observed melting temperatures is prevalent for spacer < 10 CH 2 units. The even or odd number of methylenes between acetals also affects the type and kinetics of packing assembly in layered crystallites. While a disordered mesomorphic-like structure develops under fast cooling in odd-spaced polyacetals (PA-19, PA-23), the formation of Form I crystals cannot be bypassed in PA-12 and PA-18. Furthermore, some differences are also found in the WAXD patterns of Form II between odd and even-spaced polyacetals, denoting that staggering of the acetals in the crystallites is affected by the configuration of consecutive acetals with respect to the methylene sequence.

36 MATERIALS SCIENCE↗
DOE OSTI2016

The pesticidal Cry6Aa toxin from Bacillus thuringiensis is structurally similar to HlyE-family alpha pore-forming toxins

Background: The Cry6 family of proteins from Bacillus thuringiensis represents a group of powerful toxins with great potential for use in the control of coleopteran insects and of nematode parasites of importance to agriculture. These proteins are unrelated to other insecticidal toxins at the level of their primary sequences and the structure and function of these proteins has been poorly studied to date. This has inhibited our understanding of these toxins and their mode of action, along with our ability to manipulate the proteins to alter their activity to our advantage. To increase our understanding of their mode of action and to facilitate further development of these proteins we have determined the structure of Cry6Aa in protoxin and trypsin-activated forms and demonstrated a pore-forming mechanism of action. Results: The two forms of the toxin were resolved to 2.7 Å and 2.0 Å respectively and showed very similar structures. We report Cry6Aa shows structural homology to a known class of pore-forming toxins including hemolysin E from Escherichia coli and two Bacillus cereus proteins: the hemolytic toxin HblB and the NheA component of the non-hemolytic toxin (pfam05791). Cry6Aa also shows atypical features compared to other members of this family, including internal repeat sequences and small loop regions within major alpha helices. Trypsin processing was found to result in the loss of some internal sequences while the C-terminal region remains disulfide-linked to the main core of the toxin. Based on the structural similarity of Cry6Aa to other toxins, the mechanism of action of the toxin was probed and its ability to form pores in vivo in Caenorhabditis elegans was demonstrated. A non-toxic mutant was also produced, consistent with the proposed pore-forming mode of action. Conclusions: Cry6 proteins are members of the alpha helical pore-forming toxins – a structural class not previously recognized among the Cry toxins of B. thuringiensis and representing a new paradigm for nematocidal and insecticidal proteins. Elucidation of both the structure and the pore-forming mechanism of action of Cry6Aa now opens the way to more detailed analysis of toxin specificity and the development of new toxin variants with novel activities.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2012

Form and Aging of Plutonium in Savannah River Site Waste Tank 18

Process modeling; injection molding; long-fiber thermoplastic; fiber orientation; fiber lengt This report provides a summary of the effects of aging on and the expected forms of plutonium in Tank 18 waste residues. The findings are based on available information on the operational history of Tank 18, reported analytical results for samples taken from Tank 18, and the available scientific literature for plutonium under alkaline conditions. These findings should apply in general to residues in other waste tanks. However, the operational history of other waste tanks should be evaluated for specific conditions and unique operations (e.g., acid cleaning with oxalic acid) that could alter the form of plutonium in heel residues. Based on the operational history of other tanks, characterization of samples from the heel residues in those tanks would be appropriate to confirm the form of plutonium. During the operational period and continuing with the residual heel removal periods, Pu(IV) is the dominant oxidation state of the plutonium. Small fractions of Pu(V) and Pu(VI) could be present as the result of the presence of water and the result of reactions with oxygen in air and products from the radiolysis of water. However, the presence of Pu(V) would be transitory as it is not stable at the dilute alkaline conditions that currently exists in Tank 18. Most of the plutonium that enters Savannah River Site (SRS) high-level waste (HLW) tanks is freshly precipitated as amorphous plutonium hydroxide, Pu(OH) 4(am) or hydrous plutonium oxide, PuO 2(am,hyd) and coprecipitated within a mixture of hydrous metal oxide phases containing metals such as iron, aluminum, manganese and uranium. The coprecipitated plutonium would include Pu 4+ that has been substituted for other metal ions in crystal lattice sites, Pu 4+ occluded within hydrous metal oxide particles and Pu 4+ adsorbed onto the surface of hydrous metal oxide particles. The adsorbed plutonium could include both inner sphere coordination and outer sphere coordination of the plutonium. PuO 2(am,hyd) is also likely to be present in deposits and scales that have formed on the steel surfaces of the tank. Over the operational period and after closure of Tank 18, Ostwald ripening has and will continue to transform PuO 2(am,hyd) to a more crystalline form of plutonium dioxide, PuO 2(c) . After bulk waste removal and heel retrieval operations, the free hydroxide concentration decreased and the carbonate concentration in the free liquid and solids increased. Consequently, a portion of the PuO 2(am,hyd) has likely been converted to a hydroxy-carbonate complex such as Pu(OH) 2 (CO 3 ) (s) . or PuO(CO 3 ) · xH 2 O (am) . Like PuO 2(am,hyd) , Ostwald ripening of Pu(OH) 2 (CO 3 ) (s) or PuO(CO 3 ) · xH 2 O (am) would be expected to occur to produce a more crystalline form of the plutonium carbonate complex. Due to the high alkalinity and low carbonate concentration in the grout formulation, it is expected that upon interaction with the grout, the plutonium carbonate complexes will transform back into plutonium hydroxide. Although crystalline plutonium dioxide is the more stable thermodynamic state of Pu(IV), the low temperature and high water content of the waste during the operating and heel removal periods in Tank 18 have limited the transformation of the plutonium into crystalline plutonium dioxide. During the tank closure period of thousands of years, transformation of the plutonium into a more crystalline plutonium dioxide form would be expected. However, the continuing presence of water, reaction with water radiolysis products, and low temperatures will limit the transformation, and will likely maintain an amorphous Pu(OH) 4 or PuO 2(am,hyd) form on the surface of any crystalline plutonium dioxide produced after tank closure. X-ray Absorption Spectroscopic (XAS) measurements of Tank 18 residues are recommended to confirm coordination environments of the plutonium. If the presence of PuO(CO 3 ) (am,hyd) is confirmed by XAS, it is recommended that experiments be conducted to determine if plutonium carbonates are transformed back into PuO 2(am,hyd) upon contact with grout.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2017

Updated Liquid Secondary Waste Grout Formulation and Preliminary Waste Form Qualification

This report describes the results from liquid secondary waste grout (LSWG) formulation and cementitious waste form qualification tests performed by Pacific Northwest National Laboratory (PNNL) for Washington River Protection Solutions, LLC (WRPS). New formulations for preparing a cementitious waste form from a high-sulfate liquid secondary waste stream simulant, developed for Effluent Management Facility (EMF) process condensates merged with low activity waste (LAW) caustic scrubber, and the release of key constituents (e.g. 99 Tc and 129 I) from these monoliths were evaluated. This work supports a technology development program to address the technology needs for Hanford Site Effluent Treatment Facility (ETF) liquid secondary waste (LSW) solidification and supports future Direct Feed Low-Activity Waste (DFLAW) operations. High-priority activities included simulant development, LSWG formulation, and waste form qualification. The work contained within this report relates to waste form development and testing and does not directly support the 2017 integrated disposal facility (IDF) performance assessment (PA). However, this work contains valuable information for use in PA maintenance past FY17, and for future waste form development efforts. The provided data should be used by (i) cementitious waste form scientists to further understanding of cementitious dissolution behavior, (ii) IDF PA modelers who use quantified constituent leachability, effective diffusivity, and partitioning coefficients to advance PA modeling efforts, and (iii) the U.S. Department of Energy (DOE) contractors and decision makers as they assess the IDF PA program. The results obtained help fill existing data gaps, support final selection of a LSWG waste form, and improve the technical defensibility of long-term waste form performance estimates.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2017

Effluent Management Facility Evaporator Bottom-Waste Streams Formulation and Waste Form Qualification Testing

This report describes the results from grout formulation and cementitious waste form qualification testing performed by Pacific Northwest National Laboratory (PNNL) for Washington River Protection Solutions, LLC (WRPS). These results are part of a screening test that investigates three grout formulations proposed for wide-range treatment of different waste stream compositions expected for the Hanford Effluent Management Facility (EMF) evaporator bottom waste. This work supports the technical development need for alternative disposition paths for the EMF evaporator bottom wastes and future direct feed low-activity waste (DFLAW) operations at the Hanford Site. High-priority activities included simulant production, grout formulation, and cementitious waste form qualification testing. The work contained within this report relates to waste form development and testing, and does not directly support the 2017 Integrated Disposal Facility (IDF) performance assessment (PA). However, this work contains valuable information for use in PA maintenance past FY 2017 and future waste form development efforts. The provided results and data should be used by (1) cementitious waste form scientists to further the understanding of cementitious leach behavior of contaminants of concern (COCs), (2) decision makers interested in off-site waste form disposal, and (3) the U.S. Department of Energy, their Hanford Site contractors and stakeholders as they assess the IDF PA program at the Hanford Site. The results reported help fill existing data gaps, support final selection of a cementitious waste form for the EMF evaporator bottom waste, and improve the technical defensibility of long-term waste form risk estimates.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2018

Effluent Management Facility Evaporator Bottoms: Waste Streams Formulation and Waste Form Qualification Testing

This report describes the results from grout formulation and cementitious waste form testing performed by Pacific Northwest National Laboratory for Washington River Protection Solutions, LLC (WRPS). These results are part of a screening test that investigates grout formulations proposed for encapsulating a wide range of compositions predicted to be present in evaporator bottoms wastes from the Hanford Effluent Management Facility (EMF). This work supports the technical development need for alternative treatment and disposition paths for the EMF evaporator bottoms waste and future direct-feed low-activity waste (DFLAW) operations at the Hanford Site. High-priority activities included simulant production, grout formulation, and cementitious waste form testing. The work contained within this report relates to waste form development and testing, but does not directly support the 2017 Integrated Disposal Facility (IDF) performance assessment (PA). However, this work contains information useful for future PA updates [beyond fiscal year (FY) 2017] and future waste form development efforts. These analytical results can be used by (i) cementitious waste form scientists to further the understanding of cementitious leach behavior of contaminants of concern (COCs), (ii) decision makers interested in off-site waste form disposal, and (iii) the U.S. Department of Energy, their Hanford Site contractors, and stakeholders as they continue to assess the IDF PA program at the Hanford Site. The reported results help fill existing data gaps, support final selection of a cementitious waste form for the EMF evaporator bottoms waste, and improve the technical defensibility of long-term waste form risk estimates.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗