Results for the Third Quarter 2012 Tank 50 WAC Slurry Sample: Chemical and Radionuclide Contaminants

This report details the chemical and radionuclide contaminant results for the characterization of the 2012 Third Quarter sampling of Tank 50 for the Saltstone Waste Acceptance Criteria (WAC). Information from this characterization will be used by Waste Solidification Engineering (WSE) 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

Results For The First Quarter 2012 Tank 50 WAC Slurry Sample: Chemical And Radionuclide Contaminant Results

This report details the chemical and radionuclide contaminant results for the characterization of the 2012 First Quarter sampling of Tank 50 for the Saltstone Waste Acceptance Criteria (WAC). Information from this characterization will be used by Waste Solidification Engineering (WSE) 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 memorandum: The concentrations of the reported chemical and radioactive contaminants were less than their respective WAC targets or limits unless noted; The reported detection limit for {sup 94}Nb is above the requested limit but below the estimated limit; {sup 247}Cm and {sup 249}Cf are above the requested limits. However, they are below the limits established; The reported detection limit for Norpar 13 is greater than the limit from the WAC; The reported detection limit for Isopar L is greater than the limit from WAC; 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 report are the concentrations in the sub-sample as detected by the instrument, however, the results may not accurately represent the concentrations of the analytes in Tank 50; The low insoluble solids content increases the measurement uncertainty for insoluble species

Results For The First Quarter 2012 Tank 50 WAC Slurry Sample: Chemical And Radionuclide Contaminant Results

This report details the chemical and radionuclide contaminant results for the characterization of the 2012 First Quarter sampling of Tank 50 for the Saltstone Waste Acceptance Criteria (WAC). Information from this characterization will be used by Waste Solidification Engineering (WSE) 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 memorandum: The concentrations of the reported chemical and radioactive contaminants were less than their respective WAC targets or limits unless noted; The reported detection limit for {sup 94}Nb is above the requested limit but below the estimated limit; {sup 247}Cm and {sup 249}Cf are above the requested limits. However, they are below the limits established; The reported detection limit for Norpar 13 is greater than the limit from the WAC; The reported detection limit for Isopar L is greater than the limit from WAC; 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 report are the concentrations in the sub-sample as detected by the instrument, however, the results may not accurately represent the concentrations of the analytes in Tank 50; The low insoluble solids content increases the measurement uncertainty for insoluble species

Results For The First Quarter 2013 Tank 50 WAC Slurry Sample: Chemical And Radionuclide Contaminants

This report details the chemical and radionuclide contaminant results for the characterization of the 2013 First Quarter sampling of Tank 50 for the Saltstone Waste Acceptance Criteria (WAC). Information from this characterization will be used by Waste Solidification Engineering (WSE) 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: SRR WAC targets or limits were met for all analyzed chemical and radioactive contaminates unless noted in this section; {sup 59}Ni, {sup 94}Nb, {sup 247}Cm, {sup 249}Cf, and {sup 251}Cf are above the requested SRR target concentrations. However, they are below the detection limits established by SRNL; Norpar 13 and Isopar L have higher detection limits compared with the Saltstone WAC. The data provided in this report is based upon the concentrations in the sub-sample, and due to the limited solubility in aqueous solution, may not represent the concentrations of the analytes in Tank 50; and, The low insoluble solids content increases the measurement uncertainty for insoluble species

Results For The Fourth Quarter 2012 Tank 50 WAC Slurry Sample: Chemical And Radionuclide Contaminants

This report details the chemical and radionuclide contaminant results for the characterization of the 2012 Fourth Quarter sampling of Tank 50 for the Saltstone Waste Acceptance Criteria (WAC).Information from this characterization will be used by Waste Solidification Engineering (WSE) 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: The concentration of the reported chemical and radioactive contaminants were less than their respective WAC Limits and Targets, unless noted in this section; Norpar 13 and Isopar L have higher detection limits compared with the Saltstone WAC. The data provided in this report is based upon the concentrations in the sub-sample, and due to the limited solubility in aqueous solution, may not represent the concentrations of the analytes in Tank 50; Diisooctyl adipate (or diisooctyl hexanedioate) and 5-methyl-3-hexanol, plasticizers, were measured at 1.30E+00 mg/L and 3.00E+00 mg/L, respectively, in one of two replicate measurements conducted on an at-depth sample. The organic analysis of the at-depth sample was conducted at the request of SRR. These analytes were below the detection limits for the surface sample; and, The low insoluble solids content increases the measurement uncertainty for insoluble species

Assessment of the Impact of a New Guanidine Suppressor In NGS on F/H Laboratory Analyses For DWPF and Saltstone MCU Transfers

Implementation of the Next Generation Solvent (NGS) in the Modular Caustic-Side Solvent Extraction Unit (MCU) will now proceed with a new suppressor compound, 1,2,3-tris(3,7-dimethyloctyl)guanidine (TiDG), replacing the originally planned suppressor for NGS, 1,3-dicyclohexyl-2-(11-methyldodecyl) guanidine (DCiTG). The Savannah River National Laboratory (SRNL) was tasked with evaluating the potential impact to F/H Laboratory analyses supporting the Defense Waste Processing Facility (DWPF) Waste Acceptance Criteria (WAC) used to qualify transfers of MCU Strip Effluent (SE) into the facility and the Saltstone WAC used to qualify transfers of Tank 50 containing Decontaminated Salt Solution (DSS) from MCU into Saltstone. This assigned scope is covered by a Task Technical and Quality Assurance Plan (TTQAP). Previous impact evaluations were conducted when the DCiTG suppressor was planned for NGS and concluded that there was no impact to either the determination of MCU SE pH nor the analysis of Isopar® L carryover in the MCU SE and DSS streams. SRNL reported on this series of cross-check studies between the SRNL and F/H Laboratories. The change in suppressor from DCiTG to TiDG in the NGS should not impact the measurement of Isopar® L or pH in SE or DSS necessary to satisfy DWPF and Saltstone WAC (Tank 50) criteria, respectively. A statistical study of the low bias observed in Isopar® L measurements in both SRNL and F/H Laboratories may be necessary now that the final NGS composition is fixed in order to quantify the low bias so that a proper correction can be applied to measurements critical to the DWPF and Saltstone WACs. Depending upon the final DWPF WAC requirement put in place for SE pH, it could become necessary to implement an alternative ICP-AES measurement of boron. The current blended solvent system testing in SRNL should address any impacts to Isopar® L carryover into either the DSS or the SE. It is recommended that SRNL monitor the current blended solvent work underway with simulants in SRNL as well as any DWPF CPC testing done with the new SE stream to ascertain whether any need develops that could result in modification of any currently planned F/H Laboratory testing protocols

Examination Of Sulfur Measurements In DWPF Sludge Slurry And SRAT Product Materials

Savannah River National Laboratory (SRNL) was asked to re-sample the received SB7b WAPS material for wt. % solids, perform an aqua regia digestion and analyze the digested material by inductively coupled plasma - atomic emission spectroscopy (ICP-AES), as well as re-examine the supernate by ICP-AES. The new analyses were requested in order to provide confidence that the initial analytical subsample was representative of the Tank 40 sample received and to replicate the S results obtained on the initial subsample collected. The ICP-AES analyses for S were examined with both axial and radial detection of the sulfur ICP-AES spectroscopic emission lines to ascertain if there was any significant difference in the reported results. The outcome of this second subsample of the Tank 40 WAPS material is the first subject of this report. After examination of the data from the new subsample of the SB7b WAPS material, a team of DWPF and SRNL staff looked for ways to address the question of whether there was in fact insoluble S that was not being accounted for by ion chromatography (IC) analysis. The question of how much S is reaching the melter was thought best addressed by examining a DWPF Slurry Mix Evaporator (SME) Product sample, but the significant dilution of sludge material, containing the S species in question, that results from frit addition was believed to add additional uncertainty to the S analysis of SME Product material. At the time of these discussions it was believed that all S present in a Sludge Receipt and Adjustment Tank (SRAT) Receipt sample would be converted to sulfate during the course of the SRAT cycle. A SRAT Product sample would not have the S dilution effect resulting from frit addition, and hence, it was decided that a DWPF SRAT Product sample would be obtained and submitted to SRNL for digestion and sample preparation followed by a round-robin analysis of the prepared samples by the DWPF Laboratory, F/H Laboratories, and SRNL for S and sulfate. The results of this round-robin analytical study are the second subject of this report

Investigation of Sludge Batch 3 (Macrobatch 4) Glass Sample Anomalous Behavior

Two Defense Waste Processing Facility (DWPF) glass samples from Sludge Batch 3 (SB3) (Macrobatch 4) were received by the Savannah River National Laboratory (SRNL) on February 23, 2005. One sample, S02244, was designated for the Product Consistency Test (PCT) and elemental and radionuclide analyses. The second sample, S02247, was designated for archival storage. The samples were pulled from the melter pour stream during the feeding of Melter Feed Tank (MFT) Batch 308 and therefore roughly correspond to feed from Slurry Mix Evaporator (SME) Batches 306-308. During the course of preparing sample S02244 for PCT and other analyses two observations were made which were characterized as ''unusual'' or anomalous behavior relative to historical observations of glasses prepared for the PCT. These observations ultimately led to a series of scoping tests in order to determine more about the nature of the behavior and possible mechanisms. The first observation was the behavior of the ground glass fraction (-100 +200 mesh) for PCT analysis when contacted with deionized water during the washing phase of the PCT procedure. The behavior was analogous to that of an organic compound in the presence of water: clumping, floating on the water surface, and crawling up the beaker walls. In other words, the glass sample did not ''wet'' normally, displaying a hydrophobic behavior in water. This had never been seen before in 18 years SRNL PCT tests on either radioactive or non-radioactive glasses. Typical glass behavior is largely to settle to the bottom of the water filled beaker, though there may be suspended fines which result in some cloudiness to the wash water. The typical appearance is analogous to wetting sand. The second observation was the presence of faint black rings at the initial and final solution levels in the Teflon vessels used for the mixed acid digestion of S02244 glass conducted for compositional analysis. The digestion is composed of two stages, and at both the intermediate and the final content levels in the digestion vessel the rings were present. The rings had not been seen previously during glass digestions and were not present in the Analytical Reference Glass (ARG) standard samples digested, in separate vessels, along with the DWPF glass. What follows in this report are the results and analyses from various scoping experiments done in order to explain the anomalous behavior observed with DWPF glass S02244, along with a comparison with tests on sample S02247 where the anomalous wetting behavior was not observed

SLUDGE BATCH 4 FOLLOW-UP QUALIFICATION STUDIES TO EVALUATE HYDROGEN GENERATION

Follow-up testing was conducted to better understand the excessive hydrogen generation seen in the initial Sludge Batch 4 (SB4) qualification Sludge Receipt and Adjustment Tank/Slurry Mix Evaporator (SRAT/SME) simulation in the Savannah River National Laboratory (SRNL) Shielded Cells. This effort included both radioactive and simulant work. The initial SB4 qualification test produced 0.59 lbs/hr hydrogen in the SRAT, which was just below the DWPF SRAT limit of 0.65 lbs/hr, and the test produced over 0.5 lbs/hr hydrogen in the SME cycle on two separate occasions, which were over the DWPF SME limit of 0.223 lbs/hr

DEMONSTRATION OF THE DWPF FLOWSHEET IN THE SRNL SHIELDED CELLS WITH TANK 40 AND H CANYON NEPTUNIUM

The Defense Waste Processing Facility (DWPF) is currently processing Sludge Batch 5 (SB5) from Tank 40. SB5 contains the contents of Tank 51 from November 2008, qualified by the Savannah River National Laboratory (SRNL) and the heel in Tank 40 remaining from Sludge Batch 4. Current Liquid Waste Operations (LWO) plans are to (1) decant supernatant from Tank 40 to remove excess liquid caused by a leaking slurry pump and (2) receive a Np stream from H Canyon It should be noted that the Np stream contains significant nitrate requiring addition of nitrite to Tank 40 to maintain a high nitrite to nitrate ratio for corrosion control. SRNL has been requested to qualify the proposed changes; determine the impact on DWPF processability in terms of hydrogen generation, rheology, etc.; evaluate antifoam addition strategy; and evaluate mercury stripping. Therefore, SRNL received a 3 L sample of Tank 40 following the transfer of Tank 51 to Tank 40 (Tank Farm Sample HTF-40-08-157 to be used in testing and to perform the required Waste Acceptance Product Specifications radionuclide analyses). Based on Tank Farm projections, SRNL decanted a portion* of the sample, added sodium nitrite, and added a Np solution from H Canyon representative of the Np to be dispositioned to Tank 40 (neutralized to 0.6 M excess hydroxide). The resulting material was used in a DWPF Chemical Process Cell (CPC) demonstration -- a Sludge Receipt and Adjustment Tank (SRAT) cycle and a Slurry Mix Evaporator (SME) cycle. Preliminary data from the demonstration has been reported previously. This report includes discussion of these results and additional results, including comparisons to Tank Farm projections and the SB5 demonstration