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At least 883 records · Page 49

Solidification of REDC Organics For Disposal As Solid Waste

The Radiochemical Engineering Development Center (REDC) generates various liquid organic wastes from processing irradiated targets to recover heavy elements. In the past, these organics were discharged to the Oak Ridge National Laboratory (ORNL) liquid low-level waste (LLLW) system, along with the aqueous waste. Because of a reduction in aqueous LLLW from other ORNL generators and an increase in the radionuclide concentration, particularly 238 Pu, in the REDC organic waste stream, the organics can no longer be discharged to the LLLW system. The plan is to solidify the liquid organic waste for disposal as solid waste. Solidifying the organic liquids using PM-199 Organoclay ® would produce solid waste forms with no free liquid, which should qualify for disposal at the Waste Isolation Pilot Plant. Granular Organoclay can be added to the organic waste solutions until there is a dry layer on top of the liquid and then allowed to cure for a few hours to produce a solid wasteform.

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Degradation of Simulated HLW Glass and International Simple Glass immersed partially in water - 16474

Water degradation of glass waste forms destined for geological disposal has been studied in a variety of conditions including of bulk glass immersed completely in static or dynamic water. During the course of repository life, the canisters may be only partially immersed in the initial stages of contact with water. Under these conditions glass degradation occurs on the glass immersed in water and on the glass above water by vapor condensation. In this work degradation of International Simple Glass (ISG) and Simulated High Level Waste Glass (HSG) is examined by immersing partially in distilled water during the course of test. Under static experimental conditions at 90 deg. C, the condensation of vapor on the ISG glass surface formed Ca-rich precipitates and pits after degrading for 1 and 3 weeks respectively. Whereas HSG precipitated Ca-rich phases predominantly after 1 week and no pits were found on the surface. When compared, HSG was found to change surface chemistry faster than ISG. (authors)

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Structures of fluoride containing aluminosilicate low activity nuclear waste glasses: A molecular dynamics simulations study

Fluorine and other halides commonly exist in nuclear waste forms, and due to their volatile nature, halide retention poses an issue affecting waste loading during vitrification. The compositional effect on fluorine incorporation in aluminosilicate glasses is investigated through molecular dynamics simulations. Oxygen and fluorine coordination numbers around glass former and modifier cations, bond angle distributions, and medium range structure features such as Q n distributions, ring size distributions and neutron diffraction structure factors were calculated. It was found that fluorine has higher preference to bond to Ca 2+ than to Na + , both in the melt and the glass, and there is no Si-F bond formation in the glass but they do exist in the melt. Consequently, CaO for Na 2 O substitution can be an effective way to help fluorine retention without significantly changing the glass chemistry. Furthermore, these results thus provide insights on fluorine incorporation in the aluminosilicate nuclear waste glasses and the strategy on how to improve fluorine retention both in the glass and the melt.

36 MATERIALS SCIENCE↗

Vibrational spectroscopy of uranium tetrafluoride hydrates

Uranium tetrafluoride (UF 4 ) is an important intermediate in the production of UF6 and nuclear fuel. Historical characterization of UF 4 with Raman spectroscopy was plagued with ambiguity until the first accurate Raman spectrum was published by our group in 2016. Although generally considered to be relatively stable, UF 4 can hydrolyze to form numerous UF 4 hydrates that may play a role in future uranium waste forms. In contrast to anhydrous UF 4 , the hydrates, with their OH stretch and HOH bending modes, can be spectroscopically characterized by the type and degree of water bonding in the crystal lattice, which can yield additional information about their crystal structure. Herein, vibrational spectroscopy (Raman and infrared) was used to characterize three different UF 4 hydrates: UF 4 (H 2 O) 0.33 , U 3 F 12 (H 2 O), and UF 4 (H 2 O) 2.5 . Spectra show the different hydrates vary in the number of observed bands, full-width half-maximum of the bands, and band intensity. These differences are due to varying interactions between the OH stretch and HOH bending modes with UF 4 and the polymeric UF 4 structure in the crystal lattice. These vibrational data, in combination with spectral fitting and crystallographic structures measured with powder X-ray diffraction and single crystal X-ray diffraction, provide unique details on the location of water molecules in the crystal lattice of hydrated UF 4 , and provide an interesting contrast to the vibrational spectra of anhydrous UF 4 .

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Testing of Alternative Abrasives for Water-Jet Cutting at C Tank Farm

Legacy waste from defense-related activities at the Hanford Site has predominantly been stored in underground tanks, some of which have leaked; others may be at risk to do so. The U.S. Department of Energy’s goal is to empty the tanks and transform their contents into more stable waste forms. To do so requires breaking up, and creating a slurry from, solid wastes in the bottoms of the tanks. A technology developed for this purpose is the Mobile Arm Retrieval System. This system is being used at some of the older single shell tanks at C tank farm. As originally planned, access ports for the Mobile Arm Retrieval System were to be cut using a high- pressure water-jet cutter. However, water alone was found to be insufficient to allow effective cutting of the steel-reinforced tank lids, especially when cutting the steel reinforcing bar (“rebar”). The abrasive added in cutting the hole in Tank C-107 was garnet, a complex natural aluminosilicate. The hardness of garnet (Mohs hardness ranging from H 6.5 to 7.5) exceeds that of solids currently in the tanks, and was regarded to be a threat to Hanford Waste Treatment and Immobilization Plant systems. Olivine, an iron-magnesium silicate that is nearly as hard as garnet (H 6.5 to 7), has been proposed as an alternative to garnet. Pacific Northwest National Laboratory proposed to test pyrite (FeS 2 ), whose hardness is slightly less (H 6 to 6.5) for 1) cutting effectiveness, and 2) propensity to dissolve (or disintegrate by chemical reaction) in chemical conditions similar to those of tank waste solutions. Cutting experiments were conducted using an air abrader system and a National Institute of Standards and Technology Standard Reference Material (SRM 1767 Low Alloy Steel), which was used as a surrogate for rebar. The cutting efficacy of pyrite was compared with that of garnet and olivine in identical size fractions. Garnet was found to be most effective in removing steel from the target; olivine and pyrite were less effective, but about equal to each other. The reactivity of pyrite, compared to olivine and garnet, was studied in high-pH, simulated tank waste solutions in a series of bench-top experiments. Variations in temperature, degree of agitation, grain size, exposure to air, and presence of nitrate and nitrite were also studied. Olivine and garnet showed no sign of dissolution or other reaction. Pyrite was shown to react with the fluids in even its coarsest variation (150-1000 μm). Projected times to total dissolution for most experiments range from months to ca. 12 years, and the strongest control on reaction rate is the grain size.

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Follow-On Report of Analysis of Approaches to Supplemental Treatment of Low-Activity Waste at the Hanford Nuclear Reservation (Volumes I & II)

The Hanford Site, in southeast Washington State, is preparing to disposition approximately 56,000,000 gallons (56 Mgal) of radioactive and chemically hazardous wastes currently stored in underground tanks at the site. Tank wastes will be divided into a high-activity fraction and a low-activity fraction for subsequent treatment and disposition. A waste processing and treatment facility, the Waste Treatment and Immobilization Plant (WTP), will include the high-level waste (HLW) vitrification facility (WTP HLW Vitrification Facility) for immobilizing the high-activity fraction and a low-activity waste (LAW) vitrification facility (WTP LAW Vitrification Facility) for immobilizing the low-activity fraction. Both facilities will use vitrification technology to immobilize the Hanford tank wastes in a glass waste form.

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Development in corrosion resistance by microstructural refinement in Zr-16 SS 304 alloy using suction casting technique

Highlights: • Grain refinement was made in Zr–16 wt.% SS alloy while prepared by suction casting process. • Distribution of Laves phase, e.g., Zr{sub 2}(Fe, Cr) was raised in suction cast (SC) Zr–16 wt.% SS. • Corrosion resistance was improved in SC alloy compared to that of arc-melt-cast alloy. • Grain refinement in SC alloy assisted for an increase in its corrosion resistance. - Abstract: Zirconium (Zr)-stainless steel (SS) hybrid alloys are being considered as baseline alloys for developing metallic-waste-form (MWF) with the motivation of disposing of Zr and SS base nuclear metallic wastes. Zr–16 wt.% SS, a MWF alloy optimized from previous studies, exhibit significant grain refinement and changes in phase assemblages (soft phase: Zr{sub 2}(Fe, Cr)/α-Zr vs. hard phase: Zr{sub 3}(Fe, Ni)) when prepared by suction casting (SC) technique in comparison to arc-cast-melt (AMC) route. Variation in Cr-distribution among different phases are found to be low in suction cast alloy, which along with grain refinement restricted Cr-depletion at the Zr{sub 2}(Fe, Cr)/Zr interfaces, prone to localized attack. Hence, SC alloy, compared to AMC alloy, showed lower current density, higher potential at the breakdown of passivity and higher corrosion potential during polarization experiments (carried out under possible geological repository environments, viz., pH 8, 5 and 1) indicating its superior corrosion resistance.

36 MATERIALS SCIENCE↗

Demonstration Test Report: Vacuum Thermal Desorption (VTD) Testing to Support West Area Waste Feed Test 2

Approximately 54 million gallons of radioactive and hazardous waste are stored in underground storage tanks at the U.S. Department of Energy’s (DOE’s) Hanford Site in southeastern Washington State. The Hanford Waste Treatment and Immobilization Plant (WTP) is being constructed to immobilize the waste in glass waste forms. The baseline configuration of the WTP includes a Pretreatment Facility to separate the wastes into a small volume of high-level waste (HLW) containing most of the radioactivity and a larger volume of low-activity waste (LAW) containing most of the non-radioactive chemicals. The HLW will be converted to glass in the HLW vitrification facility for ultimate disposal at a federal repository.

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Summary Report For The Analysis Of The Sludge Batch 7b (Macrobatch 9) DWPF Pour Stream Glass Sample For Canister S04023 (Rev. 1)

In order to comply with the Defense Waste Processing Facility (DWPF) Waste Form Compliance Plan for Sluldge Batch 7b, Savannah River National Laboratory (SRNL) personnel characterized the Defense Waste Processing Facility (DWPF) pour stream (PS) glass sample collected while filling canister S04023. This report summarizes the results of the compositional analysis for reportable oxides and radionuclides and the normalized Product Consistency Test (PCT) results. The PCT responses indicate that the DWPF produced glass that is significantly more durable than the Environmental Assessment glass.

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Summary Report for the Analysis of the Sludge Batch 7b (Macrobatch 9) DWPF Pour Stream Glass Sample for Canister S04023

In order to comply with the Defense Waste Processing Facility (DWPF) Waste Form Compliance Plan for Sludge Batch 7b, Savannah River National Laboratory (SRNL) personnel characterized the Defense Waste Processing Facility (DWPF) pour stream (PS) glass sample collected while filling canister S04023. This report summarizes the results of the compositional analysis for reportable oxides and radionuclides and the normalized Product Consistency Test (PCT) results. The PCT responses indicate that the DWPF produced glass that is significantly more durable than the Environmental Assessment glass. Results and further details are documented in SRNL-STI-2013-00462, Revision 1 “Analysis of the DWPF Sludge Batch 7b (Macrobatch 9) Pour Stream Glass Sample.”

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Thermal Evolution near Heat-Generating Nuclear Waste Canisters Disposed in Horizontal Drillholes

We consider the disposal of spent nuclear fuel and high-level radioactive waste in horizontal holes drilled into deep, low-permeable geologic formations using directional drilling technology. Residual decay heat emanating from these waste forms leads to temperature increases within the drillhole and the surrounding host rock. The spacing of waste canisters and the configuration of the various barrier components within the horizontal drillhole can be designed such that the maximum temperatures remain below limits that are set for each element of the engineered and natural repository system. We present design calculations that examine the thermal evolution around heat-generating waste for a wide range of material properties and disposal configurations. Moreover, we evaluate alternative layouts of a monitoring system to be part of an in situ heater test that helps determine the thermal properties of the as-built repository system. A data-worth analysis is performed to ensure that sufficient information will be collected during the heater test so that subsequent model predictions of the thermal evolution around horizontal deposition holes will reliably estimate the maximum temperatures in the drillhole. The simulations demonstrate that the proposed drillhole disposal strategy can be flexibly designed to ensure dissipation of the heat generated by decaying nuclear waste. Moreover, an in situ heater test can provide the relevant data needed to develop a reliable prediction model of repository performance under as-built conditions.

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An analysis of the technical status of high level radioactive waste and spent fuel management systems

The technical status of the old U.S. mailine program for high level radioactive nuclear waste management, and the newly-developing program for disposal of unreprocessed spent fuel was assessed. The method of long term containment for both of these waste forms is considered to be deep geologic isolation in bedded salt. Each major component of both waste management systems is analyzed in terms of its scientific feasibility, technical achievability and engineering achievability. The resulting matrix leads to a systematic identification of major unresolved technical or scientific questions and/or gaps in these programs.

English, T.↗

OPP-B332-032 Rev AD

The purpose of this procedure is to provide the approved method for converting transuranic (TRU) contaminated liquid waste into acceptable TRU waste forms.

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OPP-B332-035 Rev AD

This procedure provides instructions for converting transuranic (TRU) contaminated liquid waste into acceptable TRU waste forms.

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Process and equipment development for hot isostatic pressing treatability study

Battelle Energy Alliance (BEA), LLC, has developed processes and equipment for a pilot-scale hot isostatic pressing (HIP) treatability study to stabilize and volume reduce radioactive calcine stored at Idaho National Laboratory (INL). In 2009, the U. S. Department of Energy signed a Record of Decision with the state of Idaho selecting HIP technology as the method to treat 5,800 yd^3 (4,400 m^3) of granular zirconia and alumina calcine produced between 1953 and 1992 as a waste byproduct of spent nuclear fuel reprocessing. Since the 1990s, a variety of radioactive and hazardous waste forms have been remotely treated using HIP within INL hot cells. To execute the remote process at INL, waste is loaded into a stainless-steel or aluminum can, which is evacuated, sealed, and placed into a HIP furnace. The HIP simultaneously heats and pressurizes the waste, reducing its volume and increasing its durability. Two 1 gal cans of calcine waste currently stored in a shielded cask were identified as candidate materials for a treatability study involving the HIP process. Equipment and materials for cask-handling and calcine transfer into INL hot cells, as well as remotely operated equipment for waste can opening, particle sizing, material blending, and HIP can loading have been designed and successfully tested. These results demonstrate BEA’s readiness for treatment of INL calcine.

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Post-Closure Performance Assessment for Deep Borehole Disposal of Cs/Sr Capsules

Post-closure performance assessment (PA) calculations suggest that deep borehole disposal of cesium (Cs)/strontium (Sr) capsules, a U.S. Department of Energy (DOE) waste form (WF), is safe, resulting in no releases to the biosphere over 10,000,000 years when the waste is placed in a 3–5 km deep waste disposal zone. The same is true when a hypothetical breach of a stuck waste package (WP) is assumed to occur at much shallower depths penetrated by through-going fractures. Cs and Sr retardation in the host rock is a key control over movement. Calculated borehole performance would be even stronger if credit was taken for the presence of the WP.

58 GEOSCIENCES↗

Insights on the structure and properties of sodium iron phosphate glasses from molecular dynamics simulations

Iron phosphate glasses are promising nuclear waste forms while more detailed understanding of their structures and structure-property relations are still needed to better design waste glass compositions. In this work we report studies of three series of sodium iron phosphate (NFP) glasses: 60P 2 O 5 -(40-x)Fe 2 O 3 -xNa 2 O (x = 0→40), (100–2x)P 2 O 5 -xFe 2 O 3 -xNa 2 O (x = 5→17.5) and one with different iron redox ratio, to understand the composition as well as the iron redox effects on the structure and properties of these glasses using molecular dynamics simulations with effective two-body and three-body potentials. Structural analyses, including pair distribution function, bond angle distribution, Q n distribution, and polyhedral connectivity, were performed to obtain in-depth information on short-range and medium-range structural features. The P-O pair distributions showed a first peak splitting with phosphorus-bridging and non-bridging oxygen contributions. This and the average P-O and other cation-oxygen bond distances are in excellent agreement with experiments. The coordination number of P 5+ remained four while that of Fe 3+ increased from 4.30 to 4.72 with decreasing Fe/Na ratio. Polyhedral linkage analysis showed [PO 4 ] units linked with [PO 4 ] and [FeO x ] through corner-sharing while the [PO 4 ]-[FeO x ] linkages become dominant for compositions with Fe 2 O 3 larger than 15 mol%. The effect of iron redox ratio on the structure of NFP glasses was also studied and it was found that bond lengths and coordination numbers were not strongly affected, while the reduction of iron introduced higher network distortions, as evident by O-P-O bond angle and Q n distribution. The glass transition temperature (T g ) showed a monotonic increase with Fe 2 O 3 in the first series, in good agreement with experiments, while those of the second series showed a maximum at P 2 O 5 = 82 mol%. Here, calculated elastic moduli were found to increase with Fe 2 O 3 in the first glass series, which was be explained by the increase of network connectivity, while those of the second series decrease with Fe 2 O 3 due to decrease of P 2 O 5 .

36 MATERIALS SCIENCE↗

Inventory and Waste Characterization Status Report

This report provides an update to Sassani et al. (2016) and includes: (1) an updated set of inputs (Sections 2.3) on various additional waste forms (WF) covering both DOE-managed spent nuclear fuel (SNF) and DOE-managed (as) high-level waste (HLW) for use in the inventory represented in the geologic disposal safety analyses (GDSA); (2) summaries of evaluations initiated to refine specific characteristics of particular WF for future use (Section 2.4); (3) updated development status of the Online Waste Library (OWL) database (Section 3.1.2) and an updated user guide to OWL (Section 3.1.3); and (4) status updates (Section 3.2) for the OWL inventory content, data entry checking process, and external OWL BETA testing initiated in fiscal year 2017.

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