Ostwald Ripening and Its Effect on PuO2 Particle Size in Hanford Tank Waste

Between 1944 and 1989, the Hanford Site produced 60 percent (54.5 metric tons) of the United States weapons plutonium and produced an additional 12.9 metric tons of fuels-grade plutonium. High activity wastes, including plutonium lost from the separations processes used to isolate the plutonium, were discharged to underground storage tanks during these operations. Plutonium in the Hanford tank farms is estimated to be {approx}700 kg but may be up to {approx}1000 kg. Despite these apparent large quantities, the average plutonium concentration in the {approx}200 million liter tank waste volume is only about 0.003 grams per liter ({approx}0.0002 wt%). The plutonium is largely associated with low solubility metal hydroxide/oxide sludges where its low concentration and intimate mixture with neutron-absorbing elements (e.g., iron) are credited in nuclear criticality safety. However, concerns have been expressed that plutonium, in the form of plutonium hydrous oxide, PuO{sub 2} {center_dot} xH{sub 2}O, could undergo sufficient crystal growth through Ostwald ripening in the alkaline tank waste to potentially be separable from neutron absorbing constituents by settling or sedimentation. It was found that plutonium that entered the alkaline tank waste by precipitation through neutralization from acid solution is initially present as 2- to 3-nm (0.002- to 0.003-{mu}m) scale PuO{sub 2} {center_dot} xH{sub 2}O crystallite particles and grows from that point at exceedingly slow rates, posing no risk to physical segregation. These conclusions are reached by both general considerations of Ostwald ripening and specific observations of the behaviors of PuO{sub 2} and PuO{sub 2} {center_dot} xH{sub 2}O upon aging in alkaline solution

Strength Measurements of Archive K Basin Sludge Using a Soil Penetrometer

Spent fuel radioactive sludge present in the K East and K West spent nuclear fuel storage basins now resides in the KW Basin in six large underwater engineered containers. The sludge will be dispositioned in two phases under the Sludge Treatment Project: (1) hydraulic retrieval into sludge transport and storage containers (STSCs) and transport to interim storage in Central Plateau and (2) retrieval from the STSCs, treatment, and packaging for shipment to the Waste Isolation Pilot Plant. In the years the STSCs are stored, sludge strength is expected to increase through chemical reaction, intergrowth of sludge crystals, and compaction and dewatering by settling. Increased sludge strength can impact the type and operation of the retrieval equipment needed prior to final sludge treatment and packaging. It is important to determine whether water jetting, planned for sludge retrieval from STSCs, will be effective. Shear strength is a property known to correlate with the effectiveness of water jetting. Accordingly, the unconfined compressive strengths (UCS) of archive K Basin sludge samples and sludge blends were measured using a pocket penetrometer modified for hot cell use. Based on known correlations, UCS values can be converted to shear strengths. Twenty-six sludge samples, stored in hot cells for a number of years since last being disturbed, were identified as potential candidates for UCS measurement and valid UCS measurements were made for twelve, each of which was found as moist or water-immersed solids at least 1/2-inch deep. Ten of the twelve samples were relatively weak, having consistencies described as 'very soft' to 'soft'. Two of the twelve samples, KE Pit and KC-4 P250, were strong with 'very stiff' and 'stiff' consistencies described, respectively, as 'can be indented by a thumb nail' or 'can be indented by thumb'. Both of these sludge samples are composites collected from KE Basin floor and Weasel Pit locations. Despite both strong sludges having relatively high iron concentrations, attribution of their high strengths to this factor could not be made with confidence as other measured sludge samples, also from the KE Basin floor and of high iron concentration, were relatively weak. The observed UCS and shear strengths for the two strong sludges were greater than observed in any prior testing of K Basin sludge except for sludge processed at 185 C under hydrothermal conditions

Processing of Non-PFP Plutonium Oxide in Hanford Plants

Processing of non-irradiated plutonium oxide, PuO2, scrap for recovery of plutonium values occurred routinely at Hanford’s Plutonium Finishing Plant (PFP) in glovebox line operations. Plutonium oxide is difficult to dissolve, particularly if it has been high-fired; i.e., calcined to temperatures above about 400°C and much of it was. Dissolution of the PuO2 in the scrap typically was performed in PFP’s Miscellaneous Treatment line using nitric acid (HNO3) containing some source of fluoride ion, F-, such as hydrofluoric acid (HF), sodium fluoride (NaF), or calcium fluoride (CaF2). The HNO3 concentration generally was 6 M or higher whereas the fluoride concentration was ~0.5 M or lower. At higher fluoride concentrations, plutonium fluoride (PuF4) would precipitate, thus limiting the plutonium dissolution. Some plutonium-bearing scrap also contained PuF4 and thus required no added fluoride. Once the plutonium scrap was dissolved, the excess fluoride was complexed with aluminum ion, Al3+, added as aluminum nitrate, Al(NO3)3•9H2O, to limit collateral damage to the process equipment by the corrosive fluoride. Aluminum nitrate also was added in low quantities in processing PuF4

Characteristics of STP Pre-2004 Archived KE Basin Sludge Samples Before and After Re-Jarring in the RPL - April 2012

This report describes results of work performed in the Shielded Analytical Laboratory (SAL) at the Pacific Northwest National Laboratory’s (PNNL) Radiochemical Processing Laboratory (RPL) with archive K East (KE) Basin sludge samples obtained before the year 2004, with some of them composited and initially characterized five years ago (Delegard et al. 2011). The previously performed testing included the physical properties determinations for selected samples (settled and particle densities, water and solids concentrations), the pH, as well as identification of crystalline phases by X-ray diffractometry (XRD) for selected samples. Another objective of the previous characterization and testing campaign was to transfer some sludge composites and individual samples into new storage containers to overcome the embrittlement effect which develops in original glass containers as a result of extended exposure to high radiation fields and which increases probability of sample loss

Mitigation of Hydrogen Gas Generation from the Reaction of Uranium Metal with Water in K Basin Sludge and Sludge Waste Forms

Prior laboratory testing identified sodium nitrate and nitrite to be the most promising agents to minimize hydrogen generation from uranium metal aqueous corrosion in Hanford Site K Basin sludge. Of the two, nitrate was determined to be better because of higher chemical capacity, lower toxicity, more reliable efficacy, and fewer side reactions than nitrite. The present lab tests were run to determine if nitrate’s beneficial effects to lower H2 generation in simulated and genuine sludge continued for simulated sludge mixed with agents to immobilize water to help meet the Waste Isolation Pilot Plant (WIPP) waste acceptance drainable liquid criterion. Tests were run at ~60°C, 80°C, and 95°C using near spherical high-purity uranium metal beads and simulated sludge to emulate uranium-rich KW containerized sludge currently residing in engineered containers KW-210 and KW-220. Immobilization agents tested were Portland cement (PC), a commercial blend of PC with sepiolite clay (Aquaset II H), granulated sepiolite clay (Aquaset II G), and sepiolite clay powder (Aquaset II). In all cases except tests with Aquaset II G, the simulated sludge was mixed intimately with the immobilization agent before testing commenced. For the granulated Aquaset II G clay was added to the top of the settled sludge/solution mixture according to manufacturer application directions. The gas volumes and compositions, uranium metal corrosion mass losses, and nitrite, ammonia, and hydroxide concentrations in the interstitial solutions were measured. Uranium metal corrosion rates were compared with rates forecast from the known uranium metal anoxic water corrosion rate law. The ratios of the forecast to the observed rates were calculated to find the corrosion rate attenuation factors. Hydrogen quantities also were measured and compared with quantities expected based on non-attenuated H2 generation at the full forecast anoxic corrosion rate to arrive at H2 attenuation factors. The uranium metal corrosion rates in water alone and in simulated sludge were near or slightly below the metal-in-water rate while nitrate-free sludge/Aquaset II decreased rates by about a factor of 3. Addition of 1 M nitrate to simulated sludge decreased the corrosion rate by a factor of ~5 while 1 M nitrate in sludge/Aquaset II mixtures decreased the corrosion rate by ~2.5 compared with the nitrate-free analogues. Mixtures of simulated sludge with Aquaset II treated with 1 M nitrate had uranium corrosion rates about a factor of 8 to 10 lower than the water-only rate law. Nitrate was found to provide substantial hydrogen mitigation for immobilized simulant sludge waste forms containing Aquaset II or Aquaset II G clay. Hydrogen attenuation factors of 1000 or greater were determined at 60°C for sludge-clay mixtures at 1 M nitrate. Hydrogen mitigation for tests with PC and Aquaset II H (which contains PC) were inconclusive because of suspected failure to overcome induction times and fully enter into anoxic corrosion. Lessening of hydrogen attenuation at ~80°C and ~95°C for simulated sludge and Aquaset II was observed with attenuation factors around 100 to 200 at 1 M nitrate. Valuable additional information has been obtained on the ability of nitrate to attenuate hydrogen gas generation from solution, simulant K Basin sludge, and simulant sludge with immobilization agents. Details on characteristics of the associated reactions were also obtained. The present testing confirms prior work which indicates that nitrate is an effective agent to attenuate hydrogen from uranium metal corrosion in water and simulated K Basin sludge to show that it is also effective in potential candidate solidified K Basin waste forms for WIPP disposal. The hydrogen mitigation afforded by nitrate appears to be sufficient to meet the hydrogen generation limits for shipping various sludge waste streams based on uranium metal concentrations and assumed waste form loadings

Hydrothermal Testing of K Basin Sludge and N Reactor Fuel at Sludge Treatment Project Operating Conditions

The Sludge Treatment Project (STP), managed for the U. S. DOE by Fluor Hanford (FH), was created to design and operate a process to eliminate uranium metal from K Basin sludge prior to packaging for Waste Isolation Pilot Plant (WIPP). The STP process uses high temperature liquid water to accelerate the reaction, produce uranium dioxide from the uranium metal, and safely discharge the hydrogen. Under nominal process conditions, the sludge will be heated in pressurized water at 185°C for as long as 72 hours to assure the complete reaction (corrosion) of up to 0.25-inch diameter uranium metal pieces. Under contract to FH, the Pacific Northwest National Laboratory (PNNL) conducted bench-scale testing of the STP hydrothermal process in November and December 2006. Five tests (~50 ml each) were conducted in sealed, un-agitated reaction vessels under the hydrothermal conditions (e.g., 7 to 72 h at 185°C) of the STP corrosion process using radioactive sludge samples collected from the K East Basin and particles/coupons of N Reactor fuel also taken from the K Basins. The tests were designed to evaluate and understand the chemical changes that may be occurring and the effects that any changes would have on sludge rheological properties. The tests were not designed to evaluate engineering aspects of the process. The hydrothermal treatment affected the chemical and physical properties of the sludge. In each test, significant uranium compound phase changes were identified, resulting from dehydration and chemical reduction reactions. Physical properties of the sludge were significantly altered from their initial, as-settled sludge values, including, shear strength, settled density, weight percent water, and gas retention

Preparation and Characterization of Uranium Oxides in Support of the K Basin Sludge Treatment Project

Uraninite (UO2) and metaschoepite (UO3·2H2O) are the uranium phases most frequently observed in K Basin sludge. Uraninite arises from the oxidation of uranium metal by anoxic water and metaschoepite arises from oxidation of uraninite by atmospheric or radiolytic oxygen. Studies of the oxidation of uraninite by oxygen to form metaschoepite were performed at 21°C and 50°C. A uranium oxide oxidation state characterization method based on spectrophotometry of the solution formed by dissolving aqueous slurries in phosphoric acid was developed to follow the extent of reaction. This method may be applied to determine uranium oxide oxidation state distribution in K Basin sludge. The uraninite produced by anoxic corrosion of uranium metal has exceedingly fine particle size (6 nm diameter), forms agglomerates, and has the formula UO2.004±0.007; i.e., is practically stoichiometric UO2. The metaschoepite particles are flatter and wider when prepared at 21°C than the particles prepared at 50°C. These particles are much smaller than the metaschoepite observed in prolonged exposure of actual K Basin sludge to warm moist oxidizing conditions. The uraninite produced by anoxic uranium metal corrosion and the metaschoepite produced by reaction of uraninite aqueous slurries with oxygen may be used in engineering and process development testing. A rapid alternative method to determine uranium metal concentrations in sludge also was identified

Test Plan: Sludge Treatment Project Corrosion Process Chemistry Follow-on Testing

This test plan was prepared by the Pacific Northwest National Laboratory (PNNL) under contract with Fluor Hanford (FH). The test plan describes the scope and conditions to be used to perform laboratory-scale testing of the Sludge Treatment Project (STP) hydrothermal treatment of K Basin sludge. The STP, managed for the U. S. Department of Energy (DOE) by FH, was created to design and operate a process to eliminate uranium metal from the sludge prior to packaging for Waste Isolation Pilot Plant (WIPP) by using high temperature liquid water to accelerate the reaction, produce uranium dioxide from the uranium metal, and safely discharge the hydrogen. The proposed testing builds on the approach and laboratory test findings for both K Basin sludge and simulated sludge garnered during prior testing from September 2006 to March 2007. The outlined testing in this plan is designed to yield further understanding of the nature of the chemical reactions, the effects of compositional and process variations and the effectiveness of various strategies to mitigate the observed high shear strength phenomenon observed during the prior testing. These tests are designed to provide process validation and refinement vs. process development and design input. The expected outcome is to establish a level of understanding of the chemistry such that successful operating strategies and parameters can be implemented within the confines of the existing STP corrosion vessel design. In July 2007, the DOE provided direction to FH regarding significant changes to the scope of the overall STP. As a result of the changes, FH directed PNNL to stop work on most of the planned activities covered in this test plan. Therefore, it is unlikely the testing described here will be performed. However, to preserve the test strategy and details developed to date, the test plan has been published

Transportability Class of Americium in K Basin Sludge under Ambient and Hydrothermal Processing Conditions

This report establishes the technical bases for using a ''slow uptake'' instead of a ''moderate uptake'' transportability class for americium-241 (241Am) for the K Basin Sludge Treatment Project (STP) dose consequence analysis. Slow uptake classes are used for most uranium and plutonium oxides. A moderate uptake class has been used in prior STP analyses for 241Am based on the properties of separated 241Am and its associated oxide. However, when 241Am exists as an ingrown progeny (and as a small mass fraction) within plutonium mixtures, it is appropriate to assign transportability factors of the predominant plutonium mixtures (typically slow) to the Am241. It is argued that the transportability factor for 241Am in sludge likewise should be slow because it exists as a small mass fraction as the ingrown progeny within the uranium oxide in sludge. In this report, the transportability class assignment for 241Am is underpinned with radiochemical characterization data on K Basin sludge and with studies conducted with other irradiated fuel exposed to elevated temperatures and conditions similar to the STP. Key findings and conclusions from evaluation of the characterization data and published literature are summarized here. Plutonium and 241Am make up very small fractions of the uranium within the K Basin sludge matrix. Plutonium is present at about 1 atom per 500 atoms of uranium and 241Am at about 1 atom per 19000 of uranium. Plutonium and americium are found to remain with uranium in the solid phase in all of the {approx}60 samples taken and analyzed from various sources of K Basin sludge. The uranium-specific concentrations of plutonium and americium also remain approximately constant over a uranium concentration range (in the dry sludge solids) from 0.2 to 94 wt%, a factor of {approx}460. This invariability demonstrates that 241Am does not partition from the uranium or plutonium fraction for any characterized sludge matrix. Most of the K Basin sludge characterization data is derived spent nuclear fuel corroded within the K Basins at 10-15?C. The STP process will place water-laden sludges from the K Basin in process vessels at {approx}150-180 C. Therefore, published studies with other irradiated (uranium oxide) fuel were examined. From these studies, the affinity of plutonium and americium for uranium in irradiated UO2 also was demonstrated at hydrothermal conditions (150 C anoxic liquid water) approaching those proposed for the STP process and even for hydrothermal conditions outside of the STP operating envelope (e.g., 150 C oxic and 100 C oxic and anoxic liquid water). In summary, by demonstrating that the chemical and physical behavior of 241Am in the sludge matrix is similar to that of the predominant species (uranium and for the plutonium from which it originates), a technical basis is provided for using the slow uptake transportability factor for 241Am that is currently used for plutonium and uranium oxides. The change from moderate to slow uptake for 241Am could reduce the overall analyzed dose consequences for the STP by more than 30%

Characteristics of KE Basin Sludge Samples Archived in the RPL - 2007

Samples of sludge were collected from the K East fuel storage basin (KE Basin) floor, contiguous pits (Weasel Pit, North Load Out Pit, Dummy Elevator Pit, and Tech View Pit), and fuel storage canisters between 1995 and 2003 for chemical and radionuclide concentration analysis, physical property determination, and chemical process testing work. Because of the value of the sludge in this testing and because of the cost of obtaining additional fresh samples, an ongoing program of sludge preservation has taken place with the goals to track the sludge identities and preserve, as well as possible, the sludge composition by keeping the sludge in sealed jars and maintaining water coverage on the sludge consistent with the controlling Fluor Hanford (FH) Sampling and Analysis plans and FH contracts with the Pacific Northwest National Laboratory (PNNL). This work was originally initiated to provide material for planned hydrothermal treatment testing in accordance with the test plan for the Sludge Treatment Project (STP) corrosion process chemistry follow on testing (Delegard et al. 2007). Although most of the planned hydrothermal testing was canceled in July 2007 (as described in the forward of Delegard et al. 2007), sample consolidation and characterization was continued to identify a set of well-characterized sludge samples that are suited to support evolving STP initiatives. The work described in the letter was performed by the PNNL under the direction of the Sludge Treatment Project, managed by Fluor Hanford