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At least 397 records · Page 22

Removal of TcO 4 – from Representative Nuclear Waste Streams with Layered Potassium Metal Sulfide Materials

Many efforts have focused on the sequestration and immobilization of 99Tc because the radionuclide is highly mobile in oxidizing environments and presents serious health risks due to its radiotoxicity and long half-life (t1/2 = 213 000 a). One of the more common methods for Tc removal from solution and immobilization in solids is based on reducing Tc from highly soluble Tc(VII) to sparingly soluble Tc(IV). In order to remove solution Tc through this reduction process, the Tc-sequestering solid must contain a reducing agent and, ideally, the Tc-sequestering material would function in a large range of chemical environments. For long-term stability, the reduced Tc would preferentially be incorporated into the resulting mineral structure instead of simply being sorbed onto the mineral surface. Here, we report results obtained from batch sorption experiments performed in anoxic and oxic conditions with two sulfide-containing potassium metal sulfide (KMS) materials, known as KMS-2 and KMS-2-SS. In deionized water in anoxic conditions after 15 d of contact, KMS-2 is capable of removing ~45% of Tc and KMS-2-SS is capable of removing ~90% of Tc. The improved performance of KMS-2-SS compared to KMS-2 in deionized water in anoxic conditions appears to be linked both to a higher pH resulting from the batch sorption experiments performed with KMS-2-SS and a higher overall purity of KMS-2-SS. Both materials perform even better in highly caustic (pH~13.5), high ionic strength (8.0 M) simulated Hanford low-activity waste solutions, removing more than 90% Tc after 15 d of contact in anoxic conditions. Post-reaction solids analysis indicate that Tc(VII) is reduced to Tc(IV) and that Tc(IV) is bonded to S atoms in the resulting KMS-2 structure in a Tc2S7 form. In contrast to previous ion exchange experiments with other KMS materials, the batch sorption experiments examining Tc removal cause the initially crystalline KMS materials to lose much of their initial long-range order.

Environmental Molecular Sciences Laboratory↗

Demonstration of sulfur solubility determinations in high waste loading, low-activity waste glasses

A method recommended by Pacific Northwest National Laboratory (PNNL) for sulfate solubility determinations in simulated low-activity waste glasses was demonstrated using three compositions from a recent Hanford high waste loading glass study. Sodium and sulfate concentrations in the glasses increased after each re-melting step. Visual observations of the glasses during the re-melting process reflected the changes in composition. The measured compositions showed that the glasses met the targeted values. The amount of SO 3 retained in the glasses after washing was relatively high, ranging from 1.6 to 2.6 weight percent (wt %). Measured SnO 2 concentrations were notably low in all of the study glasses. The composition of the wash solutions should be measured in future work to determine whether SnO 2 is present with the excess sulfate washed from the glass. Increases in batch size and the amount of sodium sulfate added did not have a measureable impact on the amount of sulfate retained in the glass, although this was tested for only a single glass composition. A batch size of 250 g and a sodium sulfate addition targeting 7 wt %, as recommended by PNNL, will be used in future experiments.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Alternative Chemical Cleaning Methods for High Level Waste Tanks: Actual Waste Testing with SRS Tank 5F Sludge

Solubility testing with actual High Level Waste tank sludge has been conducted in order to evaluate several alternative chemical cleaning technologies for the dissolution of sludge residuals remaining in the tanks after the exhaustion of mechanical cleaning and sludge sluicing efforts. Tests were conducted with archived Savannah River Site (SRS) radioactive sludge solids that had been retrieved from Tank 5F in order to determine the effectiveness of an optimized, dilute oxalic/nitric acid cleaning reagent toward dissolving the bulk non-radioactive waste components. Solubility tests were performed by direct sludge contact with the oxalic/nitric acid reagent and with sludge that had been pretreated and acidified with dilute nitric acid. For comparison purposes, separate samples were also contacted with pure, concentrated oxalic acid following current baseline tank chemical cleaning methods. One goal of testing with the optimized reagent was to compare the total amounts of oxalic acid and water required for sludge dissolution using the baseline and optimized cleaning methods. A second objective was to compare the two methods with regard to the dissolution of actinide species known to be drivers for SRS tank closure Performance Assessments (PA). Additionally, solubility tests were conducted with Tank 5 sludge using acidic and caustic permanganate-based methods focused on the “targeted” dissolution of actinide species.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

FY16 Annual Accomplishments - Waste Form Development and Performance: Evaluation Of Ceramic Waste Forms - Comparison Of Hot Isostatic Pressed And Melt Processed Fabrication Methods

FY16 efforts were focused on direct comparison of multi-phase ceramic waste forms produced via melt processing and HIP methods. Based on promising waste form compositions previously devised at SRNL, simulant material was prepared at SRNL and a portion was sent to the Australian Nuclear Science and Technology Organization (ANSTO) for HIP treatments, while the remainder of the material was melt processed at SRNL. The microstructure, phase formation, elemental speciation, and leach behavior, and radiation stability of the fabricated ceramics was performed. In addition, melt-processed ceramics designed with different fractions of hollandite, zirconolite, perovskite, and pyrochlore phases were investigated. for performance and properties.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Waste Shipments to and from the Nevada National Security Site, Radioactive Waste Management Complex (Q3 Transportation Report, FY20) Transportation Report

This report satisfies the U.S. Department of Energy, National Nuclear Security Administration Nevada Field Office (NNSA/NFO) commitment to prepare a quarterly summary of waste shipments to the Nevada National Security Site (NNSS) Radioactive Waste Management Complex (RWMC) in Area 5.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Waste Reduction Network Waste Glossary

This document contains relevant industry definitions to support partners in the Better Buildings, Better Plants Waste Reduction Network. Definitions were compiled using the CalRecycle Glossary, SWANA’s Waste Glossary, the U.S. Environmental Protection Agency, the State of Washington’s Department of Ecology, the Ellen MacArthur Foundation, and Metro Oregon. Some terms contain multiple complementary definitions.

Better Buildings, waste glossary, compost, waste d↗

Optimization of sludge waste removal flowsheet at SRS through incorporation of testing and in-tank waste experience - 15262

Sludge waste removal at SRS serves two purposes: to remove the sludge for tank closure, and to provide feed for sludge processing and immobilization via vitrification. Lessons learned from previous sludge removal campaigns, in addition to testing and modeling, have led to opportunities for improvements to the overall sludge removal process, as well as marked improvements in sludge removal equipment technology and operation. Testing, modeling, and experience have led to better understanding of sludge properties and behavior during agitation and settling; the primary consideration for sludge agitation is the retention and release of radiolytic hydrogen, which must be managed in order to prevent flammability concerns in the waste tanks. Mixing devices have improved considerably, from early sluicing devices to the long-shafted slurry pumps and submersible mixer pumps currently in use at SRS, as well as ongoing development with new commercial submersible mixer pumps. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Effects of composition and canister centerline cooling on microstructure, phase distribution, and chemical durability of dehalogenated iron phosphate waste forms

This paper discusses the effects of composition and canister centerline cooling (CCC) on the microstructures, phase distribution, and chemical durability of dehalogenated iron phosphate waste forms starting from chloride-based salt simulants including KCl (Simple-1), NdCl3 (Simple-2), SrCl2 (Simple-3), LaCl3 (Simple-4), LiCl (Simple-5), CsCl (Simple-6), as well as a complex simulant containing LiCl, KCl, NaCl, CsI, SrCl2, CeCl3, and NdCl3 called ERV2. The simulants represent salt constituents present in salt wastes from electrorefiners used for electrochemical reprocessing. These salts are reacted with ammonium dihydrogen phosphate (ADP) resulting in a NH4Cl (dechlorination) byproduct that is captured and phosphate product containing oxides of the salt cations. This product is further stabilized using Fe2O3 through vitrification at higher temperatures. The results presented herein describe the properties of CCC-treated materials following dechlorination and vitrification including phase identification and quantification, elemental distributions, and chemical durabilities. The chemical durability in the CCC-cooled samples are lower durability than quenched materials for the ERV2 samples. The phases formed upon CCC cooling are very complex compositionally and microstructurally.

iron phosphate glass, iron phosphate waste forms, ↗

Cesium incorporation in hollandite-rich multiphasic ceramic waste forms

Hollandite-rich multiphase waste form compositions processed by melt-solidification and spark plasma sintering (SPS) were characterized, compared, and validated for nuclear waste incorporation. Phase identification by x-ray diffraction (XRD) and electron back-scattered diffraction (EBSD) confirmed hollandite as the major phase present in these samples along with perovskite, pyrochlore and zirconolite. Distribution of selected elements observed by wavelength dispersive spectroscopy (WDS) maps indicated that Cs formed a secondary phase during SPS processing, which was considered undesirable. On the other hand, Cs partitioned into the hollandite phase in melt-processed samples. Further analysis of hollandite structure in melt-processed composition by selected area electron diffraction (SAED) revealed ordered arrangement of tunnel ions (Ba/Cs) and vacancies, suggesting efficient Cs incorporation into the lattice.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A Review of Flow Analysis Methods for Determination of Radionuclides in Nuclear Wastes and Nuclear Reactor Coolants

The safety and security nuclear power plant operations depends on the application of the most appropriate techniques and methods of chemical analysis, where modern flow analysis methods find increasing applications. Nevetheless, the current status of development of these methods is more limited than might be expected from their authentic advantages. The main aim of this contribution is to review automated flow analysis procedures developed with various detection methods for application in the nuclear energy industry. The flow analysis methods for determination of radionuclides that have been reported to date have been primarily focused mainly on environmental applications. The needs and benefits of the application of flow methods for the monitoring of nuclear wastes and for process analysis of the primary circuit coolants of light water nuclear reactors are discussed. Application of continuous flow methods (CFA) or injection methods (FIA, SIA) of flow analysis with radiometric detection shorterns the time of analysis and improves precision of determinations due to mechanization of time-consuming operations of sample processing. The use of mass spectrometry (MS) detection enables multicomponent analyses and determination of transuranic isotopes with much better limits of detection compared to radiometric detection.

radiochemical analysis, Sequential Injection and F↗

Pilot-Scale Continuous Plug-Flow Hydrothermal Liquefaction of Food Waste for Biocrude Production

Pilot-scale hydrothermal liquefaction (HTL) of biowaste is a critical step toward commercialization of the HTL technology. Despite many HTL studies conducted with wet biomass, including food waste, few were performed with a pilot-scale continuous plug-flow reactor (PFR), with the biocrude yield and quality analysis based on dewatering (ASTM D2892 Annex X1). This paper describes the development and performance evaluation of a mobile pilot-scale HTL continuous PFR, with a processing capacity of 60 L/h of wet feedstock and 6 L/h of biocrude production. The reactor system was designed for reaction conditions of up to 325 °C and 17.25 MPa. The reactor has a volume of 28.88 L with an additional counterflow heat exchanger volume of 18.07 L. Two types of food wastes, from a food processing plant and grocery store, were processed at 280 °C for 30 min, producing biocrude oil yields of 52.19 and 47.06 wt %, energy recoveries of 68.17 and 70.77%, and carbon recoveries of 66.91 and 64.78%, respectively. Furthermore, due to its high feedstock capacity and reaction volume, large amounts of biocrude oil and post-HTL wastewater (PHW) were obtained from this pilot-scale reactor to allow downstream research on upgrading biocrude oil for transportation fuel as well as PHW treatment and nutrient recovery.

09 BIOMASS FUELS↗

Nanohybrid of Cu2O-Ti3C2Tx as a Silver-Free MXene Sorbent for Iodine Gas Capture from Nuclear Waste

The capture of volatile radioiodine from nuclear fuel reprocessing off-gas streams remains a critical challenge due to the high volatility, long half-life of 129I, and biological uptake of iodide from the environment. Although silver-based sorbents provide strong iodine chemisorption, their high cost and regulatory classification as mixed radioactive-hazardous waste motivate the development of alternative materials. Here, we report a silver-free Cu2O-Ti3C2Tx MXene hybrid for iodine gas capture at 150 °C. Structural and compositional analyses confirm the formation of Cu2O nanoparticles on Ti3C2Tx nanosheets and their subsequent conversion to thermodynamically stable CuI upon static iodine gas exposure, achieving an iodine mass loading of up to 1115 mg/g. These results demonstrate the potential of Cu2O-Ti3C2Tx MXene as a copper-based alternative to silver sorbents for elevated-temperature iodine gas capture.

iodine gas capture↗

Modeling Geologic Waste Repository Systems Below Residual Saturation

The heat generated by high-level radioactive waste can pose numerical and physical challenges to subsurface flow and transport simulators if the liquid water content in a region near the waste package approaches residual saturation due to evaporation. Here, residual saturation is the fraction of the pore space occupied by liquid water when the hydraulic connectivity through a porous medium is lost, preventing the flow of liquid water. While conventional capillary pressure models represent residual saturation using asymptotically large values of capillary pressure, here, residual saturation is effectively modeled as a tortuosity effect alone. Treating the residual fluid as primarily dead-end pores and adsorbed films, relative permeability is independent of capillary pressure below residual saturation. To test this approach, PFLOTRAN is then used to simulate thermal-hydrological conditions resulting from direct disposal of a dual-purpose canister in unsaturated alluvium using both conventional asymptotic and revised, smooth models. Importantly, while the two models have comparable results over 100 000 years, the number of flow steps required is reduced by approximately 94%.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗