Elemental Composition of a Composite of Samples HTF-E-03-162 to 164 From Tank 51H to Evaluate Acceptability of the Sludge for Transfer to Tank 40H and Processing in the DWPF

Three dip samples of suspended sludge slurry were obtained from Tank 51H and sent to the Savannah River Technology Center for analysis. The composite of these samples is intended as a confirmatory sample to evaluate the acceptability of the Tank 51H sludge slurry for transfer to Tank 40H and for eventual processing in the Defense Waste Processing Facility. This report presents results of analyses requested by the Defense Waste Processing Facility for this evaluation. These analyses included the measurement of the concentrations of twenty two elements in the sludge slurry and the determination of the weight percent calcined solids of the slurry

RESULTS FOR THE SECOND QUARTER 2010 TANK 50 WAC SLURRY SAMPLE: CHEMICAL AND RADIONUCLIDE CONTAMINANT RESULTS

This report details the chemical and radionuclide contaminant results for the characterization of the 2010 Second Quarter sampling of Tank 50 for the Saltstone Waste Acceptance Criteria (WAC).1 Information from this characterization will be used by Liquid Waste Operations (LWO) to support the transfer of low-level aqueous waste from Tank 50 to the Salt Feed Tank in the Saltstone Facility in Z-Area, where the waste will be immobilized. This information is also used to update the Tank 50 Waste Characterization System. The following conclusions are drawn from the analytical results provided in this report: (1) The concentrations of the reported chemical and radioactive contaminants were less than their respective WAC targets or limits unless noted in this section. (2) The reported detection limits for {sup 94}Nb and {sup 144}Ce are above both the established and requested limits from References 4 and 6. (3) The reported detection limits for {sup 247}Cm and {sup 249}Cf are above the requested limits from Reference 4. However, they are below the limits established in Reference 6. (4) The reported detection limit for Isopar L is greater than the limit from Table 3 of the WAC. (5) A measurable concentration of Norpar 13 is present in the sample. The reported concentration is greater than the requested limit from Table 4 and Attachment 8.2 of the WAC. (6) Isopar L and Norpar 13 have limited solubility in aqueous solutions making it difficult to obtain consistent and reliable sub-samples. The values reported in this memo are the concentrations in the sub-sample as detected by the GC/MS; however, the results may not accurately represent the concentrations of the analytes in Tank 50. (7) The detection limit for isopropanol has been lowered from 0.5 mg/L to 0.25 mg/L{sup 7}. This revised limit now satisfies the limit in Table 4 of the WAC

CHARACTERIZATION OF DWPF MELTER OFF-GAS QUENCHER AND STEAM ATOMIZED SCRUBBER DEPOSIT SAMPLES

This report summarizes the results from the characterization of deposits from the inlets of the primary off-gas Quencher and Steam Atomized Scrubber (SAS) in the Defense Waste Processing Facility (DWPF), as requested by a technical assistance request. DWPF requested elemental analysis and compound identification to help determine the potential causes for the substance formation. This information will be fed into Savannah River National Laboratory modeling programs to determine if there is a way to decrease the formation of the deposits. The general approach to the characterization of these samples included x-ray diffraction (XRD), scanning electron microscopy (SEM), and chemical analysis. The following conclusions are drawn from the analytical results found in this report: (1) The deposits are not high level waste glass from the DWPF melt pool based on comparison of the compositions of deposits to the composition of a sample of glass taken from the pour stream of the melter during processing of Sludge Batch 3. (2) Chemical composition results suggest that the deposits are probably a combination of sludge and frit particles entrained in the off-gas. (3) Gamma emitters, such as Co-60, Cs-137, Eu-154, Am-241, and Am-243 were detected in both the Quencher and SAS samples with Cs-137 having the highest concentration of the gamma emitters. (4) No evidence existed for accumulation of fissile material (U-233, U-235, and Pu-239) relative to Fe in either deposit. (5) XRD results indicated both samples were primarily amorphorous and contained some crystals of the iron oxides, hematite and magnetite (Fe{sub 2}O{sub 3} and Fe(Fe{sub 2}O{sub 4})), along with sodium nitrate (NaNO{sub 3}). The other main crystalline compound in the SAS deposit was mercurous chloride. The main crystalline compound in the Quencher deposit was a uranium oxide compound. These are all sludge components. (6) SEM analysis of the Quencher deposit revealed crystalline uranium compounds within the sample. SEM analysis of the SAS sample could not be performed due to the presence of a significant concentration of Hg in the sample. (7) Essentially all the Na and the S in the off-gas samples were soluble in water. (8) The main soluble anion was NO{sub 3}{sup -} with SO{sub 4}{sup 2-} being second. (9) In contrast to the results for the off-gas deposits analyzed in 2003, soluble compounds of fluoride and chloride were detected; however, their concentrations in the Quencher and SAS deposits were less than one weight percent. (10) The results suggest that the S is primarily in the deposits as the sulfate anion

RESULTS FOR THE THIRD QUARTER 2007 TANK 50H WAC SLURRY SAMPLE: CHEMICAL AND RADIONUCLIDE CONTAMINANT RESULTS

The Saltstone Facility is designed and permitted to immobilize and dispose of low-level radioactive and hazardous liquid waste (salt solution) remaining from the processing of radioactive material at the Savannah River Site. Low activity wastewater streams from the Effluent Treatment Project (ETP), H-Canyon, and the high level waste (HLW) storage tanks, are stored as a mixture in Tank 50H until it can be pumped to the Saltstone Facility for treatment and disposal. Specific waste acceptance criteria (WAC) must be met for the transfer of low-level aqueous waste from Tank 50H to the Saltstone Facility. Low level waste which meets the WAC can be transferred, stored and treated in the Saltstone Production Facility (SPF) for subsequent disposal as saltstone in the Saltstone Disposal Facility (SDF). Waste Solidification Engineering (WSE) has requested through a Technical Task Request (TTR) that the Savannah River National Laboratory (SRNL) measure the concentrations of chemical and radionuclide contaminants listed in the currently approved Saltstone Waste Acceptance Criteria (WAC). A Task Technical and Quality Assurance Plan and Analytical Study Plan has been written for this request. WAC determinations are needed on a quarterly basis for chemical contaminants and every first and third quarter for radioactive contaminants. This memorandum presents the results for the chemical and radionuclide contaminants in the third quarter, from the samples taken from Tank 50 in September, 2007

DETERMINATION OF REPORTABLE RADIONUCLIDES FOR DWPF SLUDGE BATCH 5 (MACROBATCH 6)

The Waste Acceptance Product Specifications (WAPS) 1.2 require that ''The Producer shall report the inventory of radionuclides (in Curies) that have half-lives longer than 10 years and that are, or will be, present in concentrations greater than 0.05 percent of the total inventory for each waste type indexed to the years 2015 and 3115''. As part of the strategy to comply with WAPS 1.2, the Defense Waste Processing Facility (DWPF) will report for each waste type, all radionuclides (with half-lives greater than 10 years) that have concentrations greater than 0.01 percent of the total inventory from time of production through the 1100 year period from 2015 through 3115. The initial listing of radionuclides to be included is based on the design-basis glass as identified in the Waste Form Compliance Plan (WCP) and Waste Form Qualification Report (WQR). However, it is required that this list be expanded if other radionuclides with half-lives greater than 10 years are identified that may meet the greater than 0.01% criterion for Curie content. Specification 1.6 of the WAPS, International Atomic Energy Agency (IAEA) Safeguards Reporting for High Level Waste (HLW), requires that the ratio by weights of the following uranium and plutonium isotopes be reported: U-233, U-234, U-235, U-236, U-238, Pu-238, Pu-239, Pu-240, Pu-241, and Pu-242. Therefore, the complete set of reportable radionuclides must also include this set of U and Pu isotopes. The DWPF is receiving radioactive sludge slurry from HLW Tank 40. The radioactive sludge slurry in Tank 40 is a blend of the heel from Tank 40 (Sludge Batch 4 (SB4)), Sludge Batch 5 (SB5) that was transferred to Tank 40 from Tank 51, and H-Canyon Np transfers completed after the start of processing. The blend of sludge in Tank 40 is also referred to as Macrobatch 6 (MB6). This report develops the list of reportable radionuclides and associated activities and determines the radionuclide activities as a function of time. The DWPF will use this list and the activities as one of the inputs for the development of the Production Records that relate to the radionuclide inventory. This work was initiated through Technical Task Request (TTR) HLW-DWPF-TTR-2008-0010; Rev. 2 entitled Sludge Batch 5 SRNL Shielded Cells Testing. Specifically, this report details results from performing Subtask II, 5 of the TTR and, in part, meets Deliverable 7 of the TTR. The work was performed following the Task Technical and Quality Assurance Plan (TTQAP), WSRC-RP-2008-00137, Rev. 2 and Analytical Study Plan (ASP), WSRC-RP-2008-00138, Rev. 2. In order to determine the reportable radionuclides for SB5 (MB6), a list of radioisotopes that may meet the criteria as specified by the Department of Energy's (DOE) WAPS was developed. All radioactive U-235 fission products and all radioactive activation products that could be in the SRS HLW were considered. In addition, all U and Pu isotopes identified in WAPS 1.6 were included in the list. This list was then evaluated and some isotopes excluded from the projection calculations. Based on measurements and analytical detection limits, twenty-six radionuclides have been identified as reportable for DWPF SB5 as specified by WAPS 1.2. The 26 reportable radionuclides are: Cl-36, Ni-59, Ni-63, Sr-90, Zr-93, Nb-93m, Tc-99, Sn-126, Cs-137, Sm-151, U-233, U-234, Np-237, U-238, Pu-238, Pu-239, Pu-240, Am-241, Pu-241, Pu-242, Am-242m, Am-243, Cm-244, Cm-245, Cm-246, Cf-251. Chlorine-36 is reported for the first time based on the upper bounding activity determined from the aqua regia digested sludge slurry. The WCP and WQR require that all of radionuclides present in the Design Basis glass be considered as the initial set of reportable radionuclides. For SB5 (MB6), all of the radionuclides in the Design Basis glass are reportable except for four radionuclides: Se-79, Pd-107, Cs-135, and Th-230. At no time through the year 3115 did any of these three radionuclides contribute to more than 0.01% of the radioactivity on a Curie basis. Two additional uranium isotopes (U-235 and -236) must be added to the list of reportable radionuclides in order to meet WAPS 1.6. All of the Pu isotopes and other U isotopes (U-233, -234, and -238) identified in WAPS 1.6 were already determined to be reportable according to WAPS 1.2 This brings the total number of reportable radionuclides for SB5 to 28. The radionuclide measurements made for SB5 are the most extensive conducted to date. Some method development/refinement occurred during the conduct of these measurements, leading to lower detection limits and more accurate measurement of some isotopes than was previously possible. Continuous improvement in the analytical measurements will likely continue, and this in turn should lead to improved detection limit values for some radionuclides and actual measurements for still others

Sludge Batch 6 Acceptance Evaluation: Radionuclide Concentrations in Tank 51 sb6 Qualification Sample Prepared at SRNL

Presented in this report are radionuclide concentrations required as part of the program of qualifying Sludge Batch Six (SB6) for processing in the Defense Waste Processing Facility (DWPF). The SB6 material is currently in Tank 51 being washed and prepared for transfer to Tank 40. The acceptance evaluation needs to be completed prior to the transfer of the material in Tank 51 to Tank 40. The sludge slurry in Tank 40 has already been qualified for DWPF and is currently being processed as SB5. The radionuclide concentrations were measured or estimated in the Tank 51 SB6 Qualification Sample prepared at Savannah River National Laboratory (SRNL). This sample was prepared from the three liter sample of Tank 51 sludge slurry (HTF-51-09-110) taken on October 8, 2009. The sample was delivered to SRNL where it was initially characterized in the Shielded Cells. Under the direction of the Liquid Waste Organization it was then modified by eight washes, nine decants, an addition of Pu from Canyon Tank 16.3, and an addition of NaNO{sub 2}. This final slurry now has a composition expected to be similar to that of the slurry in Tank 51 after final preparations have been made for transfer of that slurry to Tank 40. Determining the radionuclide concentrations in this Tank 51 SB6 Qualification Sample is part of the work requested in Technical Task Request (TTR) No. HLW-DWPF-TTR-2009-0014. The work with this qualification sample is covered by a Task Technical and Quality Assurance Plan and an Analytical Study Plan. The radionuclides included in this report are needed for the DWPF Radiological Program Evaluation, the DWPF Waste Acceptance Criteria (TSR/WAC) Evaluation, and the DWPF Solid Waste Characterization Program (TTR Task I.2). Radionuclides required to meet the Waste Acceptance Product Specifications (TTR Task II.2.) will be measured at a later date after the slurry from Tank 51 has been transferred to Tank 40. Then a sample of the as-processed SB6 will be taken and transferred to SRNL for measurement of these radionuclides. The results presented in this report are those necessary for DWPF to assess if the Tank 51 SB6 sample prepared at SRNL meets the requirements for the DWPF Radiological Program Evaluation, the DWPF Waste Acceptance Criteria evaluation, and the DWPF Solid Waste Characterization Program. The sample is the same as that on which the chemical composition was reported. Concentrations are given for thirty-four radionuclides along with total alpha and beta activity. Values for total gamma and total gamma plus beta activities are also calculated. Results also indicate that 99% of the Tc-99 and at least 90% of the I-129 that could have been in this sludge batch have been removed by chemical processing steps in the SRS Canyons or Tank Farm

Leaching Tc-99 from SRP glass in simulated tuff and salt groundwaters

Results of leach tests with Tc-99 doped SRP borosilicate waste glass are presented. The glass was prepared by melting a mixture of SRP 165 powdered frit doped with a carrier free solution of Tc-99 at 1150{sup 0}C. Dissolution of portions of the resulting glass indicated that the Tc-99 was distributed homogeneously throughout the glass. Static leach tests up to 90 days were performed at 90{sup 0}C in J-13 tuff groundwater or WIPP brine A at a SA/V of 100m{sup -1}. Normalized mass losses were calculated for Tc-99 as well as all the major elements in the glass. Results indicated that under ambient oxidizing conditions Tc-99 leached no faster than the glass-forming elements of the glass. In J-13 water, Tc-99 leached congruently with B. In WIPP brine A, it leached congruently with Si. Leach rates for Li were higher in both groundwaters, probably due to a contribution from an ion exchange mechanism. Leach tests were performed under reducing conditions in J-13 water by adding Zn/Hg amalgam to the leachate. In these tests the pH increased significantly, probably because of the reaction of the amalgam with the water. In a 21-day test, the pH increased to 13 and leach rates for the glass were very high. Even though there was signifcant dissolution of the glass, the normalized mass loss based on Tc-99 was only 0.02g/m{sup 2}. This result and the fact that reducing conditions at normal pH values do not significantly affect the dissolution of the glass, indicate that the low concentrations for Tc-99 obtained under reducing conditions are due to is solubility and not due to an increased durability of the glass. 14 refs., 2 figs., 5 tabs

PLUTONIUM SOLUBILITY IN HIGH-LEVEL WASTE ALKALI BOROSILICATE GLASS

The solubility of plutonium in a Sludge Batch 6 (SB6) reference glass and the effect of incorporation of Pu in the glass on specific glass properties were evaluated. A Pu loading of 1 wt % in glass was studied. Prior to actual plutonium glass testing, surrogate testing (using Hf as a surrogate for Pu) was conducted to evaluate the homogeneity of significant quantities of Hf (Pu) in the glass, determine the most appropriate methods to evaluate homogeneity for Pu glass testing, and to evaluate the impact of Hf loading in the glass on select glass properties. Surrogate testing was conducted using Hf to represent between 0 and 1 wt % Pu in glass on an equivalent molar basis. A Pu loading of 1 wt % in glass translated to {approx}18 kg Pu per Defense Waste Processing Facility (DWPF) canister, or about 10X the current allowed limit per the Waste Acceptance Product Specifications (2500 g/m{sup 3} of glass or about 1700 g/canister) and about 30X the current allowable concentration based on the fissile material concentration limit referenced in the Yucca Mountain Project License Application (897 g/m{sup 3}3 of glass or about 600 g Pu/canister). Based on historical process throughput data, this level was considered to represent a reasonable upper bound for Pu loading based on the ability to provide Pu containing feed to the DWPF. The task elements included evaluating the distribution of Pu in the glass (e.g. homogeneity), evaluating crystallization within the glass, evaluating select glass properties (with surrogates), and evaluating durability using the Product Consistency Test -- Method A (PCT-A). The behavior of Pu in the melter was evaluated using paper studies and corresponding analyses of DWPF melter pour samples.The results of the testing indicated that at 1 wt % Pu in the glass, the Pu was homogeneously distributed and did not result in any formation of plutonium-containing crystalline phases as long as the glass was prepared under 'well-mixed' conditions. The incorporation of 1 wt % Pu in the glass did not adversely impact glass viscosity (as assessed using Hf surrogate) or glass durability. Finally, evaluation of DWPF glass pour samples that had Pu concentrations below the 897 g/m{sup 3} limit showed that Pu concentrations in the glass pour stream were close to targeted compositions in the melter feed indicating that Pu neither volatilized from the melt nor stratified in the melter when processed in the DWPF melter

DETERMINATION OF REPORTABLE RADIONUCLIDES FOR DWPF SLUDGE BATCH 4 MACROBATCH 5

The Waste Acceptance Product Specifications (WAPS)1 1.2 require that 'The Producer shall report the inventory of radionuclides (in Curies) that have half-lives longer than 10 years and that are, or will be, present in concentrations greater than 0.05 percent of the total inventory for each waste type indexed to the years 2015 and 3115'. As part of the strategy to meet WAPS 1.2, the Defense Waste Processing Facility (DWPF) will report for each waste type, all radionuclides (with half-lives greater than 10 years) that have concentrations greater than 0.01 percent of the total inventory from time of production through the 1100 year period from 2015 through 3115. The initial listing of radionuclides to be included is based on the design-basis glass as identified in the Waste Form Compliance Plan (WCP)2 and Waste Form Qualification Report (WQR)3. However, it is required that this list be expanded if other radionuclides with half-lives greater than 10 years are identified that may meet the greater than 0.01% criterion for Curie content. Specification 1.6 of the WAPS, International Atomic Energy Agency (IAEA) Safeguards Reporting for High Level Waste (HLW), requires that the ratio by weights of the following uranium and plutonium isotopes be reported: U-233, U-234, U-235, U-236, U-238, Pu-238, Pu-239, Pu-240, Pu-241, and Pu-242. Therefore, the complete set of reportable radionuclides must also include this set of U and Pu isotopes. The DWPF is receiving radioactive sludge slurry from HLW Tank 40. The radioactive sludge slurry in Tank 40 is a blend of the previous contents of Tank 40 (Sludge Batch 3) and the sludge that was transferred to Tank 40 from Tank 51. The blend of sludge from Tank 51 and Tank 40 defines Sludge Batch 4 (also referred to as Macrobatch 5 (MB5)). This report develops the list of reportable radionuclides and associated activities and determines the radionuclide activities as a function of time. The DWPF will use this list and the activities as one of the inputs for the development of the Production Records that relate to the radionuclide inventory. This work was initiated through Task Technical Request HLW/DWPF/TTR-2005-0034; Rev. 0 entitled Sludge Batch 4 SRNL Shielded Cells Testing4. Specifically, this report details results from performing, in part, Subtask 3 of the TTR and, in part, meets Deliverable 7 of the TTR. The work was performed following the Technical Task and Quality Assurance Plan (TTQAP), WSRC-RP-2006-00310, Rev. 15 and Analytical Study Plan (ASP), WSRC-RP-2006-00458, Rev. 16. In order to determine the reportable radionuclides for Sludge Batch 4 (SB4) (Macro Batch 5 (MB5)), a list of radioisotopes that may meet the criteria as specified by the Department of Energy's (DOE) WAPS was developed. All radioactive U-235 fission products and all radioactive activation products that could be in the SRS HLW were considered. In addition, all U and Pu isotopes identified in WAPS 1.6 were included in the list. This list was then evaluated and some isotopes excluded from the projection calculations. Based on measurements and analytical detection limits, twenty-nine radionuclides have been identified as reportable for DWPF SB4 (MB5) as specified by WAPS 1.2. The 29 reportable nuclides are: Ni-59; Ni-63; Se-79; Sr-90; Zr-93; Nb-93m; Tc-99; Sn-126; Cs-137; Sm-151; U-233; U-234; Np-237; U-238; Pu-238; Pu-239; Pu-240; Am-241; Pu-241; Pu-242; Am-242m; Am-243; Cm-244; Cm-245; Cm-246; Cm-247; Bk-247; Cm-248; and Cf-251. The WCP and WQR require that all of radionuclides present in the Design Basis glass be considered as the initial set of reportable radionuclides. For SB4 (MB5), all of the radionuclides in the Design Basis glass are reportable except for three radionuclides: Pd-107, Cs-135, and Th-230. At no time through the calendar year 3115 did any of these three radionuclides contribute to more than 0.01% of the radioactivity on a Curie basis. Two additional uranium isotopes (U-235 and -236) must be added to the list of reportable radionuclides in order to meet WAPS 1.6. All of the Pu isotopes and other U isotopes (U-233, -234, and -238) identified in WAPS 1.6 were already determined to be reportable according to WAPS 1.2 This brings the total number of reportable radionuclides for SB4 to thirty-one. The radionuclide measurements made for SB4 (MB5) are the most extensive conducted to date. Some method development/refinement occurred during the conduct of these measurements, leading to lower detection limits and more accurate measurement of some isotopes than was previously possible. Continuous improvement in the analytical measurements will likely continue, and this in turn should lead to improved detection limit values for some radionuclides and actual measurements for still others