VERIFICATION OF THE DEFENSE WASTE PROCESSING FACILITY'S (DWPF) PROCESS DIGESTION METHOD FOR THE SLUDGE BATCH 7A QUALIFICATION SAMPLE

For each sludge batch that is processed in the Defense Waste Processing Facility (DWPF), the Savannah River National Laboratory (SRNL) performs confirmation of the applicability of the digestion method to be used by the DWPF lab for elemental analysis of Sludge Receipt and Adjustment Tank (SRAT) receipt samples and SRAT product process control samples. DWPF SRAT samples are typically dissolved using a room temperature HF-HNO{sub 3} acid dissolution (i.e., DWPF Cold Chem Method, see DWPF Procedure SW4-15.201) and then analyzed by inductively coupled plasma - atomic emission spectroscopy (ICP-AES). This report contains the results and comparison of data generated from performing the Aqua Regia (AR), Sodium peroxide/Hydroxide Fusion (PF) and DWPF Cold Chem (CC) method digestions of Sludge Batch 7a (SB7a) SRAT Receipt and SB7a SRAT Product samples. The SB7a SRAT Receipt and SB7a SRAT Product samples were prepared in the SRNL Shielded Cells, and the SRAT Receipt material is representative of the sludge that constituates the SB7a Batch or qualification composition. This is the sludge in Tank 51 that is to be transferred into Tank 40, which will contain the heel of Sludge Batch 6 (SB6), to form the Sb7a Blend composition

Development Of Ion Chromatography Methods To Support Testing Of The Glycolic Acid Reductant Flowsheet In The Defense Waste Processing Facility

Ion Chromatography (IC) is the principal analytical method used to support studies of Sludge Reciept and Adjustment Tank (SRAT) chemistry at DWPF. A series of prior analytical ''Round Robin'' (RR) studies included both supernate and sludge samples from SRAT simulant, previously reported as memos, are tabulated in this report.2,3 From these studies it was determined to standardize IC column size to 4 mm diameter, eliminating the capillary column from use. As a follow on test, the DWPF laboratory, the PSAL laboratory, and the AD laboratory participated in the current analytical RR to determine a suite of anions in SRAT simulant by IC, results also are tabulated in this report. The particular goal was to confirm the laboratories ability to measure and quantitate glycolate ion. The target was + or - 20% inter-lab agreement of the analyte averages for the RR. Each of the three laboratories analyzed a batch of 12 samples. For each laboratory, the percent relative standard deviation (%RSD) of the averages on nitrate, glycolate, and oxalate, was 10% or less. The three laboratories all met the goal of 20% relative agreement for nitrate and glycolate. For oxalate, the PSAL laboratory reported an average value that was 20% higher than the average values reported by the DWPF laboratory and the AD laboratory. Because of this wider window of agreement, it was concluded to continue the practice of an additional acid digestion for total oxalate measurement. It should also be noted that large amounts of glycolate in the SRAT samples will have an impact on detection limits of near eluting peaks, namely Fluoride and Formate. A suite of scoping experiments are presented in the report to identify and isolate other potential interlaboratory disceprancies. Specific ion chromatography inter-laboratory method conditions and differences are tabulated. Most differences were minor but there are some temperature control equipment differences that are significant leading to a recommendation of a heated jacket for analytical columns that are remoted for use in radiohoods. A suggested method improvement would be to implement column temperture control at a temperature slightly above ambient to avoid peak shifting due to temperature fluctuations. Temperature control in this manner would improve short and longer term peak retention time stability. An unknown peak was observed during the analysis of glycolic acid and SRAT simulant. The unknown peak was determined to best match diglycolic acid. The development of a method for acetate is summaraized, and no significant amount of acetate was observed in the SRAT products tested. In addition, an alternative Gas Chromatograph (GC) method for glycolate is summarized

CHARACTERIZATION AND ALUMINUM DISSOLUTION DEMONSTRATION WITH A 3 LITER TANK 51H SAMPLE

A 3-liter sludge slurry sample was sent to SRNL for demonstration of a low temperature aluminum dissolution process. The sludge was characterized before and after the aluminum dissolution. Post aluminum dissolution sludge settling and the stability of the decanted supernate were also observed. The characterization of the as-received 3-liter sample of Tank 51H sludge slurry shows a typical high aluminum HM sludge. The XRD analysis of the dried solids indicates Boehmite is the predominant crystalline form of aluminum in the sludge solids. However, amorphous phases of aluminum present in the sludge would not be identified using this analytical technique. The low temperature (55 C) aluminum dissolution process was effective at dissolving aluminum from the sludge. Over the three week test, {approx}42% of the aluminum was dissolved out of the sludge solids. The process appears to be selective for aluminum with no other metals dissolving to any appreciable extent. At the termination of the three week test, the aluminum concentration in the supernate had not leveled off indicating more aluminum could be dissolved from the sludge with longer contact times or higher temperatures. The slow aluminum dissolution rate in the test may indicate the dissolution of the Boehmite form of aluminum however; insufficient kinetic data exists to confirm this hypothesis. The aluminum dissolution process appears to have minimal impact on the settling rate of the post aluminum dissolution sludge. However, limited settling data were generated during the test to quantify the effects. The sludge settling was complete after approximately twelve days. The supernate decanted from the settled sludge after aluminum dissolution appears stable and did not precipitate aluminum over the course of several months. A mixture of the decanted supernate with Tank 11 simulated supernate was also stable with respect to precipitation

WASHING AND DEMONSTRATION OF THE DWPF FLOWSHEET IN THE SRNL SHIELDED CELLS USING POST ALUMINUM DISSOLUTION TANK 51 SLUDGE SLURRY

The remaining contents of Tank 51 from Sludge Batch 4 will be blended with Purex sludge from Tank 7 to constitute Sludge Batch 5 (SB5). The Savannah River Site (SRS) Liquid Waste Organization (LWO) has completed caustic addition to Tank 51 to perform low temperature Al dissolution on the H-Modified (HM) sludge material to reduce the total mass of sludge solids and Al being fed to the Defense Waste Processing Facility (DWPF). The Savannah River National Lab (SRNL) has also completed aluminum dissolution tests using a 3-L sample of Tank 51 sludge slurry through funding by DOE EM-21. This report documents assessment of downstream impacts of the aluminum dissolved sludge, which were investigated so technical issues could be identified before the start of SB5 processing. This assessment included washing the aluminum dissolved sludge to a Tank Farm projected sodium concentration and weight percent insoluble solids content and DWPF Chemical Process Cell (CPC) processing using the washed sludge. Based on the limited testing, the impact of aluminum dissolution on sludge settling is not clear. Settling was not predictable for the 3-L sample. Compared to the post aluminum dissolution sample, settling after the first wash was slower, but settling after the second wash was faster. For example, post aluminum dissolution sludge took six days to settle to 60% of the original sludge slurry height, while Wash 1 took nearly eight days, and Wash 2 only took two days. Aluminum dissolution did impact sludge rheology. A comparison between the as-received, post aluminum dissolution and washed samples indicate that the downstream materials were more viscous and the concentration of insoluble solids less than that of the starting material. This increase in viscosity may impact Tank 51 transfers to Tank 40. The impact of aluminum dissolution on DWPF CPC processing cannot be determined because acid addition for the Sludge Receipt and Adjustment Tank (SRAT) cycle was under-calculated and thus under-added. Although the sludge was rheologically thick throughout the SRAT and Slurry Mix Evaporator (SME) cycles, this may have been due to the under addition of acid. Aluminum dissolution did, however, impact analyses of the SRAT receipt material. Two methods for determining total base yielded significantly different results. The high hydroxide content and the relatively high soluble aluminum content of the washed post aluminum dissolution sludge likely contributed to this difference and the ultimate under addition of acid. It should be noted that the simulant used to provide input for the SRAT cycle was an inadequate representation of the waste in terms of acid demand, likely due to the differences in the form of aluminum and hydroxide in the simulant and actual waste. Based on the results of this task, it is recommended that: (1) Sludge settling and rheology during washing of the forthcoming Sludge Batch 5 qualification sample be monitored closely and communicated to the Tank Farm. (2) SRNL receive a sample of Tank 51 after all chemical additions have been made and prior to the final Sludge Batch 5 decant for rheological assessment. Rheology versus wt% insoluble solids will be performed to determine the maximum amount of decant prior to the Tank 51 to Tank 40 transfer. (3) As a result of the problem with measuring total base and subsequently under-calculating acid for the DWPF CPC processing of the post aluminum dissolution sludge; (4) Studies to develop understanding of how the sludge titrates (i.e., why different titration methods yield different results) should be performed. (5) Simulants that better match the properties of post aluminum dissolution sludge should be developed. (6) Work on developing an acid calculation less dependant on the total base measurement should be continued

Microwave Imaging for Neoadjuvant Chemotherapy Monitoring: Initial Clinical Experience

Introduction: Microwave tomography recovers images of tissue dielectric properties, which appear to be specific for breast cancer, with low-cost technology that does not present an exposure risk, suggesting the modality may be a good candidate for monitoring neoadjuvant chemotherapy. Methods: Eight patients undergoing neoadjuvant chemotherapy for locally advanced breast cancer were imaged longitudinally five to eight times during the course of treatment. At the start of therapy, regions of interest (ROIs) were identified from contrast-enhanced magnetic resonance imaging studies. During subsequent microwave examinations, subjects were positioned with their breasts pendant in a coupling fluid and surrounded by an immersed antenna array. Microwave property values were extracted from the ROIs through an automated procedure and statistical analyses were performed to assess short term (30 days) and longer term (four to six months) dielectric property changes. Results: Two patient cases (one complete and one partial response) are presented in detail and demonstrate changes in microwave properties commensurate with the degree of treatment response observed pathologically. Normalized mean conductivity in ROIs from patients with complete pathological responses was significantly different from that of partial responders (P value = 0.004). In addition, the normalized conductivity measure also correlated well with complete pathological response at 30 days (P value = 0.002). Conclusions: These preliminary findings suggest that both early and late conductivity property changes correlate well with overall treatment response to neoadjuvant therapy in locally advanced breast cancer. This result is consistent with earlier clinical outcomes that lesion conductivity is specific to differentiating breast cancer from benign lesions and normal tissue

SLUDGE WASHING AND DEMONSTRATION OF THE DWPF FLOWSHEET IN THE SRNL SHIELDED CELLS FOR SLUDGE BATCH 5 QUALIFICATION

Sludge Batch 5 (SB5) is predominantly a combination of H-modified (HM) sludge from Tank 11 that underwent aluminum dissolution in late 2007 to reduce the total mass of sludge solids and aluminum being fed to the Defense Waste Processing Facility (DWPF) and Purex sludge transferred from Tank 7. Following aluminum dissolution, the addition of Tank 7 sludge and excess Pu to Tank 51, Liquid Waste Operations (LWO) provided the Savannah River National Laboratory (SRNL) a 3-L sample of Tank 51 sludge for SB5 qualification. SB5 qualification included washing the sample per LWO plans/projections (including the addition of a Pu/Be stream from H Canyon), DWPF Chemical Process Cell (CPC) simulations, waste glass fabrication (vitrification), and waste glass chemical durability evaluation. This report documents: (1) The washing (addition of water to dilute the sludge supernatant) and concentration (decanting of supernatant) of the Tank 51 qualification sample to adjust sodium content and weight percent insoluble solids to Tank Farm projections. (2) The performance of a DWPF CPC simulation using the washed Tank 51 sample. This includes a Sludge Receipt and Adjustment Tank (SRAT) cycle, where acid is added to the sludge to destroy nitrite and remove mercury, and a Slurry Mix Evaporator (SME) cycle, where glass frit is added to the sludge in preparation for vitrification. The SME cycle also included replication of five canister decontamination additions and concentrations. Processing parameters for the CPC processing were based on work with a non radioactive simulant. (3) Vitrification of a portion of the SME product and Product Consistency Test (PCT) evaluation of the resulting glass. (4) Rheology measurements of the initial slurry samples and samples after each phase of CPC processing. This work is controlled by a Task Technical and Quality Assurance Plan (TTQAP) , and analyses are guided by an Analytical Study Plan. This work is Technical Baseline Research and Development (R&D) for the DWPF

DEMONSTRATION OF THE DWPF FLOWSHEET IN THE SRNL SHIELDED CELLS USING ARP PRODUCT SIMULANT AND SB4 TANK 40 SLUDGE SLURRY

The radioactive startup of two new SRS processing facilities, the Actinide Removal Process (ARP) and the Modular Caustic-Side-Solvent-Extraction Unit (MCU) will add two new waste streams to the Defense Waste Processing Facility (DWPF). The ARP will remove actinides from the 5.6 M salt solution resulting in a sludge-like product that is roughly half monosodium titanate (MST) insoluble solids and half sludge insoluble solids. The ARP product will be added to the Sludge Receipt and Adjustment Tank (SRAT) at boiling and dewatered prior to pulling a SRAT receipt sample. The cesium rich MCU stream will be added to the SRAT at boiling after both formic and nitric acid have been added and the SRAT contents concentrated to the appropriate endpoint. A concern was raised by an external hydrogen review panel that the actinide loaded MST could act as a catalyst for hydrogen generation (Mar 15, 2007 report, Recommendation 9). Hydrogen generation, and it's potential to form a flammable mixture in the off-gas, under SRAT and Slurry Mix Evaporator (SME) processing conditions has been a concern since the discovery that noble metals catalyze the decomposition of formic acid. Radiolysis of water also generates hydrogen, but the radiolysis rate is orders of magnitude lower than the noble metal catalyzed generation. As a result of the concern raised by the external hydrogen review panel, hydrogen generation was a prime consideration in this experiment. Testing was designed to determine whether the presence of the irradiated ARP simulant containing MST caused uncontrolled or unexpected hydrogen production during experiments simulating the DWPF Chemical Process Cell (CPC) due to activation of titanium. A Shielded Cells experiment, SC-5, was completed using SB4 sludge from Tank 405 combined with an ARP product produced from simulants by SRNL researchers. The blend of sludge and MST was designed to be prototypic of planned DWPF SRAT and SME cycles. As glass quality was not an objective in this experiment, no vitrification of the SME product was completed. The results from this experiment were compared to the results from experiment SC-1, a similar experiment with SB4 sludge without added ARP product. This report documents: (1) The preparation and subsequent composition of the ARP product. (2) The preparation and subsequent compositional characterization of the SRAT Receipt sample. Additional details will be presented concerning the noble metal concentration of the ARP product and the SRAT receipt sample. Also, calculations related to the amount of formic and nitric acid added during SRAT processing will be presented as excess formic acid will lead to additional hydrogen generation. (3) Highlights from processing during the SRAT cycle and SME cycle (CPC processing). Hydrogen generation will be discussed since this was the prime objective for this experiment. (4) A comparison of CPC processing between SC-1 (without ARP simulant) and SC-5. This work was controlled by a Task Technical and Quality Assurance Plan (TTQAP)6, and analyses were guided by an Analytical Sample Support Matrix (ASSM)7. This Research and Development (R&D) was completed to support operation of DWPF