Anne E. Kozelisky

High-resolution solid-state nuclear magnetic resonance experiments on highly radioactive ceramics

A triple-containment magic-angle spinning rotor insert system has been developed and a sample handling procedure formulated for safely analyzing highly radioactive solids by high-resolution solid-state NMR. The protocol and containment system have been demonstrated for magic-angle spinning (MAS) experiments on ceramic samples containing 5–10 wt % 239Pu and 238Pu at rotation speeds of 3500 Hz. The technique has been used to demonstrate that MAS NMR experiments can be used to measure amorphous atomic number fractions produced by accelerated internal radiation damage. This will allow incorporated α-emitters with short half-lives to be used to model the long-term radiation tolerance of potential ceramic radioactive waste forms. This is an example of MAS NMR spectroscopy on samples containing fissionable isotopes.

Filtration and Leach Testing for REDOX Sludge and S-Saltcake Actual Waste Sample Composites

A testing program evaluating actual tank waste was developed in response to Task 4 from the M-12 External Flowsheet Review Team (EFRT) issue response plan.( ) The test program was subdivided into logical increments. The bulk water-insoluble solid wastes that are anticipated to be delivered to the Waste Treatment and Immobilization Plant (WTP) were identified according to type such that the actual waste testing could be targeted to the relevant categories. Under test plan TP-RPP-WTP-467, eight broad waste groupings were defined. Samples available from the 222S archive were identified and obtained for testing. Under this test plan, a waste-testing program was implemented that included: • Homogenizing the archive samples by group as defined in the test plan • Characterizing the homogenized sample groups • Performing parametric leaching testing on each group for compounds of interest • Performing bench-top filtration/leaching tests in the hot cell for each group to simulate filtration and leaching activities if they occurred in the UFP2 vessel of the WTP Pretreatment Facility. This report focuses on filtration/leaching tests performed on two of the eight waste composite samples and follow-on parametric tests to support aluminum leaching results from those tests.

Tc Reductant Chemistry and Crucible Melting Studies with Simulated Hanford Low-Activity Waste

The FY 2003 risk assessment (RA) of bulk vitrification (BV) waste packages used 0.3 wt% of the technetium (Tc) inventory as a leachable salt and found it sufficient to create a significant peak in the groundwater concentration in a 100-meter down-gradient well. Although this peak met regulatory limits, considering uncertainty in the actual Tc salt fraction, peak concentrations could exceed the maximum concentration limit (MCL) under some scenarios so reducing the leachable salt inventory is desirable. The main objective of this study was to reduce the mobile Tc species available within a BV disposal package by reducing the oxidation state of the Tc in the waste feed and/or during melting because Tc in its reduced form of Tc(IV) has a much lower volatility than Tc(VII). Reduced Tc volatility has a secondary benefit of increasing the Tc retention in glass.

Radiation Damage in Titanate Ceramics for Plutonium Immobilization

Results from radiation damage experiments are discussed with respect to the immobilization of Pu declared excess to the weapons programs. The ceramics are titanate-based.

Characterization and Leach Testing for PUREX Cladding Waste Sludge (Group 3) and REDOX Cladding Waste Sludge (Group 4) Actual Waste Sample Composites

A testing program evaluating actual tank waste was developed in response to Task 4 from the M-12 External Flowsheet Review Team (EFRT) issue response plan.(a) The testing program was subdivided into logical increments. The bulk water-insoluble solid wastes that are anticipated to be delivered to the Waste Treatment and Immobilization Plant (WTP) were identified according to type such that the actual waste testing could be targeted to the relevant categories. Eight broad waste groupings were defined. Samples available from the 222S archive were identified and obtained for testing. The actual wastetesting program included homogenizing the samples by group, characterizing the solids and aqueous phases, and performing parametric leaching tests. Two of the eight defined groups—plutonium-uranium extraction (PUREX) cladding waste sludge (Group 3, or CWP) and reduction-oxidation (REDOX) cladding waste sludge (Group 4, or CWR)—are the subjects of this report. Both the Group 3 and 4 waste composites were anticipated to be high in gibbsite, requiring caustic leaching. Characterization of the composite Group 3 and Group 4 waste samples confirmed them to be high in gibbsite. The focus of the Group 3 and 4 testing was on determining the behavior of gibbsite during caustic leaching. The waste-type definition, archived sample conditions, homogenization activities, characterization (physical, chemical, radioisotope, and crystal habit), and caustic leaching behavior as functions of time, temperature, and hydroxide concentration are discussed in this report. Testing was conducted according to TP-RPP-WTP-467.

The Status of Radiation Damage Experiments

Experiments have been on-going for about two years to determine the effects that radiation damage have on the physical and chemical properties of candidate titanate ceramics for the immobilization of plutonium. We summarize the results of these experiments in this document.

Nitrogen Trifluoride-Based Fluoride- Volatility Separations Process: Initial Studies

This document describes the results of our investigations on the potential use of nitrogen trifluoride as the fluorinating and oxidizing agent in fluoride volatility-based used nuclear fuel reprocessing. The conceptual process uses differences in reaction temperatures between nitrogen trifluoride and fuel constituents that produce volatile fluorides to achieve separations and recover valuable constituents. We provide results from our thermodynamic evaluations, thermo-analytical experiments, kinetic models, and provide a preliminary process flowsheet. The evaluations found that nitrogen trifluoride can effectively produce volatile fluorides at different temperatures dependent on the fuel constituent.

Filtration and Leach Testing for PUREX Cladding Sludge and REDOX Cladding Sludge Actual Waste Sample Composites

A testing program evaluating actual tank waste was developed in response to Task 4 from the M-12 External Flowsheet Review Team (EFRT) issue response plan (Barnes and Voke 2006). The test program was subdivided into logical increments. The bulk water-insoluble solid wastes that are anticipated to be delivered to the Hanford Waste Treatment and Immobilization Plant (WTP) were identified according to type such that the actual waste testing could be targeted to the relevant categories. Under test plan TP RPP WTP 467 (Fiskum et al. 2007), eight broad waste groupings were defined. Samples available from the 222S archive were identified and obtained for testing. Under this test plan, a waste testing program was implemented that included: • Homogenizing the archive samples by group as defined in the test plan. • Characterizing the homogenized sample groups. • Performing parametric leaching testing on each group for compounds of interest. • Performing bench-top filtration/leaching tests in the hot cell for each group to simulate filtration and leaching activities if they occurred in the UFP2 vessel of the WTP Pretreatment Facility. This report focuses on a filtration/leaching test performed using two of the eight waste composite samples. The sample groups examined in this report were the plutonium-uranium extraction (PUREX) cladding waste sludge (Group 3, or CWP) and reduction-oxidation (REDOX) cladding waste sludge (Group 4, or CWR). Both the Group 3 and 4 waste composites were anticipated to be high in gibbsite, thus requiring caustic leaching. WTP RPT 167 (Snow et al. 2008) describes the homogenization, characterization, and parametric leaching activities before benchtop filtration/leaching testing of these two waste groups. Characterization and initial parametric data in that report were used to plan a single filtration/leaching test using a blend of both wastes. The test focused on filtration testing of the waste and caustic leaching for aluminum, in the form of gibbsite, and its impact on filtration. The initial sample was diluted with a liquid simulant to simulate the receiving concentration of retrieved tank waste into the UFP2 vessel (< 10 wt% undissolved solids). Filtration testing was performed on the dilute waste sample and dewatered to a higher solids concentration. Filtration testing was then performed on the concentrated slurry. Afterwards, the slurry was caustic leached to remove aluminum present in the undissolved solid present in the waste. The leach was planned to simulate leaching conditions in the UFP2 vessel. During the leach, slurry supernate samples were collected to measure the dissolution rate of aluminum in the waste. After the slurry cooled down from the elevated leach temperature, the leach liquor was dewatered from the solids. The remaining slurry was rinsed and dewatered with caustic solutions to remove a majority of the dissolved aluminum from the leached slurry. The concentration of sodium hydroxide in the rinse solutions was high enough to maintain the solubility of the aluminum in the dewatered rinse solutions after dilution of the slurry supernate. Filtration tests were performed on the final slurry to compare to filtration performance before and after caustic leaching.

Thermal Stability Studies of Candidate Decontamination Agents for Hanford’s Plutonium Finishing Plant Plutonium-Contaminated Gloveboxes

This report provides the results of PNNLs and Fluors studies of the thermal stabilities of potential wastes arising from decontamination of Hanfords Plutonium Finishing Plants plutonium contaminated gloveboxes. The candidate wastes arising from the decontamination technologies ceric nitrate/nitric acid, RadPro, Glygel, and Aspigel.

Effects of Self Irradiation from 238Pu on Candidate Ceramics for Plutonium Immobilization

In this document, we describe the results of radiation damage testing and characterization for specimens that were resintered to re-establish crystallinity. The phases in these specimens have become amorphous from radiation induced damage over the 8 months since sintering.