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At least 181 records · Page 10

Detection efficiency of a water condensation particle counter using electrically neutral sulfuric acid and sulfuric acid-dimethylamine clusters

Recent advances in condensation particle counters (CPCs) have improved the detection of sub-3 nm particles, increasing the accuracy of new particle formation (NPF) measurements. However, the detection efficiencies for neutrally charged, atmospherically relevant, sub-1 nm particles, which are critical for the accurate derivation of atmospheric NPF rates, are currently unknown. Here, this study presents a method to measure the detection efficiency of sulfuric acid and clusters of sulfuric acid and dimethylamine using measured CPC concentrations and modeled cluster distributions at atmospherically relevant concentrations. This study finds that water-based CPCs can measure these clusters at detection efficiencies relevant to NPF studies.

Cheng, Darren [Carnegie Mellon Univ., Pittsburgh, ↗

A Framework for Assessing Operational Madden–Julian Oscillation Forecasts: A CLIVAR MJO Working Group Project

The U.S. Climate Variability and Predictability (CLIVAR) MJO Working Group (MJOWG) has taken steps to promote the adoption of a uniform diagnostic and set of skill metrics for analyzing and assessing dynamical forecasts of the MJO. Here we describe the framework and initial implementation of the approach using real-time forecast data from multiple operational numerical weather prediction (NWP) centers. The objectives of this activity are to provide a means to i) quantitatively compare skill of MJO forecasts across operational centers, ii) measure gains in forecast skill over time by a given center and the community as a whole, and iii) facilitate the development of a multimodel forecast of the MJO. The MJO diagnostic is based on extensive deliberations among the MJOWG in conjunction with input from a number of operational centers and makes use of the MJO index of Wheeler and Hendon. This forecast activity has been endorsed by the Working Group on Numerical Experimentation (WGNE), the international body that fosters the development of atmospheric models for NWP and climate studies. The Climate Prediction Center (CPC) within the National Centers for Environmental Prediction (NCEP) is hosting the acquisition of the forecast data, application of the MJO diagnostic, and real-time display of the standardized forecasts. The activity has contributed to the production of 1–2-week operational outlooks at NCEP and activities at other centers. Further enhancements of the diagnostic's implementation, including more extensive analysis, comparison, illustration, and verification of the contributions from the participating centers, will increase the usefulness and application of these forecasts and potentially lead to more skillful predictions of the MJO and indirectly extratropical and other weather variability (e.g., tropical cyclones) influenced by the MJO. The purpose of this article is to inform the larger scientific and operational forecast communities of the MJOWG forecast effort and invite participation from additional operational centers.

58 GEOSCIENCES↗

Evaluation of CMIP5 Model Precipitation Using PERSIANN-CDR

Abstract The purpose of this study is to use the PERSIANN–Climate Data Record (PERSIANN-CDR) dataset to evaluate the ability of 32 CMIP5 models in capturing the behavior of daily extreme precipitation estimates globally. The daily long-term historical global PERSIANN-CDR allows for a global investigation of eight precipitation indices that is unattainable with other datasets. Quantitative comparisons against CPC daily gauge; GPCP One-Degree Daily (GPCP1DD); and TRMM 3B42, version 7 (3B42V7), datasets show the credibility of PERSIANN-CDR to be used as the reference data for global evaluation of CMIP5 models. This work uniquely defines different study regions by partitioning global land areas into 25 groups based on continent and climate zone type. Results show that model performance in warm temperate and equatorial regions in capturing daily extreme precipitation behavior is largely mixed in terms of index RMSE and correlation, suggesting that these regions may benefit from weighted model averaging schemes or model selection as opposed to simple model averaging. The three driest climate regions (snow, polar, and arid) exhibit high correlations and low RMSE values when compared against PERSIANN-CDR estimates, with the exceptions of the cold regions showing an inability to capture the 95th and 99th percentile annual total precipitation characteristics. A comprehensive assessment of each model’s performance in each continent–climate zone defined group is provided as a guide for both model developers to target regions and processes that are not yet fully captured in certain climate types, and for climate model output users to be able to select the models and/or the study areas that may best fit their applications of interest.

Nguyen, Phu↗

THE IMPACT OF THE MCU LIFE EXTENSION SOLVENT ON DWPF GLASS FORMULATION EFFORTS

As a part of the Actinide Removal Process (ARP)/Modular Caustic Side Solvent Extraction Unit (MCU) Life Extension Project, a next generation solvent (NG-CSSX), a new strip acid, and modified monosodium titanate (mMST) will be deployed. The strip acid will be changed from dilute nitric acid to dilute boric acid (0.01 M). Because of these changes, experimental testing with the next generation solvent and mMST is required to determine the impact of these changes in 512-S operations as well as Chemical Process Cell (CPC), Defense Waste Processing Facility (DWPF) glass formulation activities, and melter operations at DWPF. To support programmatic objectives, the downstream impacts of the boric acid strip effluent (SE) to the glass formulation activities and melter operations are considered in this study. More specifically, the impacts of boric acid additions to the projected SB7b operating windows, potential impacts to frit production temperatures, and the potential impact of boron volatility are evaluated. Although various boric acid molarities have been reported and discussed, the baseline flowsheet used to support this assessment was 0.01M boric acid. The results of the paper study assessment indicate that Frit 418 and Frit 418-7D are robust to the implementation of the 0.01M boric acid SE into the SB7b flowsheet (sludge-only or ARP-added). More specifically, the projected operating windows for the nominal SB7b projections remain essentially constant (i.e., 25-43 or 25-44% waste loading (WL)) regardless of the flowsheet options (sludge-only, ARP added, and/or the presence of the new SE). These results indicate that even if SE is not transferred to the Sludge Receipt and Adjustment Tank (SRAT), there would be no need to add boric acid (from a trim tank) to compositionally compensate for the absence of the boric acid SE in either a sludge-only or ARP-added SB7b flowsheet. With respect to boron volatility, the Measurement Acceptability Region (MAR) assessments also suggest that Slurry Mix Evaporator (SME) acceptability decisions would not be different assuming either 100% of the B{sub 2}O{sub 3} from the SE were retained or volatilized. More specifically, the 0.84 wt% B{sub 2}O{sub 3} in the SE is so minor that its presence in the SME analysis does not influence SME acceptability decisions. In fact, using the 100% retention and 100% volatilization composition projections, only minor differences in the predicted properties of the glass product occur with all of the glasses being acceptable over a WL interval of 32-42%. Based on the 0.01M boric acid flowsheet, there is very little difference between Frit 418 and Frit 418-7D (a frit that was compositionally altered to account for the 0.84 wt% B{sub 2}O{sub 3} in the SE) with respect to melt temperature. In fact, when one evaluates the composition of Frit 418-7D, it lies within the current Frit 418 vendor specifications and therefore could have been produced by the vendor targeting the nominal composition of Frit 418.

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GLYCOLIC-FORMIC ACID FLOWSHEET SLUDGE MATRIX STUDY

Testing was completed to demonstrate the viability of the newly developed glycolic acid/formic acid flowsheet on processing in the Defense Waste Processing Facility's (DWPF) Chemical Process Cell (CPC). The Savannah River National Laboratory (SRNL) initiated a sludge matrix study to evaluate the impact of changing insoluble solid composition on the processing characteristics of slurries in DWPF. Four sludge simulants were prepared to cover two compositional ranges in the waste. The first was high iron/low aluminum versus low iron/high aluminum (referred to as HiFe or LoFe in this report). The second was high calcium-manganese/low nickel, chromium, and magnesium versus low calcium-manganese/high nickel, chromium, and magnesium (referred to as HiMn or LoMn in this report). These two options can be combined to form four distinct sludge compositions. The sludge matrix study called for testing each of these four simulants near the minimum acid required for nitrite destruction (100% acid stoichiometry) and at a second acid level that produced significant hydrogen by noble metal catalyzed decomposition of formic acid (150% acid stoichiometry). Four simulants were prepared based on the four possible combinations of the Al/Fe and Mn-Ca/Mg-Ni-Cr options. Preliminary simulant preparation work has already been documented. The four simulants were used for high and low acid testing. Eight planned experiments (GF26 to GF33) were completed to demonstrate the viability of the glycolic-formic flowsheet. Composition and physical property measurements were made on the SRAT product. Composition measurements were made on the condensate from the Mercury Water Wash Tank (MWWT), Formic Acid Vent Condenser (FAVC), ammonia scrubber and on SRAT samples pulled throughout the SRAT cycle. Updated values for formate loss and nitrite-tonitrate conversion were found that can be used in the acid calculations for future sludge matrix process simulations with the glycolic acid/formic acid flowsheet. Preliminary results of the initial testing indicate: (1) Hydrogen generation rate was very low throughout all SRAT cycles. (2) The mercury concentration of the SRAT product was below the 0.8 wt% limit in all runs. (3) Nitrite in the SRAT product was <100 mg/kg for all runs. (4) Foaminess was not an issue using the nominal antifoam addition strategy in these tests. (5) The high aluminum sludges (LoFe, HM type sludges) were much more viscous than the Hi Fe sludges. At 100% acid stoichiometry, the SRAT products from the high aluminum sludges were very viscous but at 150% acid stoichiometry, the SRAT products from the high aluminum sludges were very thin. This makes the glycolic acid/formic acid flowsheet an improvement for processing more viscous sludges. (6) The pH of the SRAT products was from 2.7-3.1 for the 150% acid stoichiometry runs and 5.1-6.1 for the 100% acid stoichiometry runs, significantly lower than is typical of the baseline nitric acid/formic acid flowsheet.

08 HYDROGEN↗

MAR ASSESSMENTS OF THE HIGH LEVEL WASTE SYSTEM PLAN REVISION 16

High-level waste (HLW) throughput (i.e., the amount of waste processed per unit of time) is primarily a function of two critical parameters: waste loading (WL) and melt rate. For the Defense Waste Processing Facility (DWPF), increasing HLW throughput would significantly reduce the overall mission life cycle costs for the Department of Energy (DOE). Significant increases in waste throughput have been achieved at DWPF since initial radioactive operations began in 1996. Key technical and operational initiatives that supported increased waste throughput included improvements in facility attainment, the Chemical Processing Cell (CPC) flowsheet, process control models and frit formulations. As a result of these key initiatives, DWPF increased WLs from a nominal 28% for Sludge Batch 2 (SB2) to {approx}34 to 38% for SB3 through SB6 while maintaining or slightly improving canister fill times. Although considerable improvements in waste throughput have been obtained, future contractual waste loading targets are nominally 40%, while canister production rates are also expected to increase (to a rate of 325 to 400 canisters per year). Although implementation of bubblers have made a positive impact on increasing melt rate for recent sludge batches targeting WLs in the mid30s, higher WLs will ultimately make the feeds to DWPF more challenging to process. Savannah River Remediation (SRR) recently requested the Savannah River National Laboratory (SRNL) to perform a paper study assessment using future sludge projections to evaluate whether the current Process Composition Control System (PCCS) algorithms would provide projected operating windows to allow future contractual WL targets to be met. More specifically, the objective of this study was to evaluate future sludge batch projections (based on Revision 16 of the HLW Systems Plan) with respect to projected operating windows using current PCCS models and associated constraints. Based on the assessments, the waste loading interval over which a glass system (i.e., a projected sludge composition with a candidate frit) is predicted to be acceptable can be defined (i.e., the projected operating window) which will provide insight into the ability to meet future contractual WL obligations. In this study, future contractual WL obligations are assumed to be 40%, which is the goal after all flowsheet enhancements have been implemented to support DWPF operations. For a system to be considered acceptable, candidate frits must be identified that provide access to at least 40% WL while accounting for potential variation in the sludge resulting from differences in batch-to-batch transfers into the Sludge Receipt and Adjustment Tank (SRAT) and/or analytical uncertainties. In more general terms, this study will assess whether or not the current glass formulation strategy (based on the use of the Nominal and Variation Stage assessments) and current PCCS models will allow access to compositional regions required to targeted higher WLs for future operations. Some of the key questions to be considered in this study include: (1) If higher WLs are attainable with current process control models, are the models valid in these compositional regions? If the higher WL glass regions are outside current model development or validation ranges, is there existing data that could be used to demonstrate model applicability (or lack thereof)? If not, experimental data may be required to revise current models or serve as validation data with the existing models. (2) Are there compositional trends in frit space that are required by the PCCS models to obtain access to these higher WLs? If so, are there potential issues with the compositions of the associated frits (e.g., limitations on the B{sub 2}O{sub 3} and/or Li{sub 2}O concentrations) as they are compared to model development/validation ranges or to the term 'borosilicate' glass? If limitations on the frit compositional range are realized, what is the impact of these restrictions on other glass properties such as the ability to suppress nepheline formation or influence melt rate? The model based assessments being performed make the assumption that the process control models are applicable over the glass compositional regions being evaluated. Although the glass compositional region of interest is ultimately defined by the specific frit, sludge, and WL interval used, there is no prescreening of these compositional regions with respect to the model development or validation ranges which is consistent with current DWPF operations.

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SLUDGE BATCH 7B QUALIFICATION ACTIVITIES WITH SRS TANK FARM SLUDGE

Waste Solidification Engineering (WSE) has requested that characterization and a radioactive demonstration of the next batch of sludge slurry - Sludge Batch 7b (SB7b) - be completed in the Shielded Cells Facility of the Savannah River National Laboratory (SRNL) via a Technical Task Request (TTR). This characterization and demonstration, or sludge batch qualification process, is required prior to transfer of the sludge from Tank 51 to the Defense Waste Processing Facility (DWPF) feed tank (Tank 40). The current WSE practice is to prepare sludge batches in Tank 51 by transferring sludge from other tanks. Discharges of nuclear materials from H Canyon are often added to Tank 51 during sludge batch preparation. The sludge is washed and transferred to Tank 40, the current DWPF feed tank. Prior to transfer of Tank 51 to Tank 40, SRNL typically simulates the Tank Farm and DWPF processes with a Tank 51 sample (referred to as the qualification sample). With the tight schedule constraints for SB7b and the potential need for caustic addition to allow for an acceptable glass processing window, the qualification for SB7b was approached differently than past batches. For SB7b, SRNL prepared a Tank 51 and a Tank 40 sample for qualification. SRNL did not receive the qualification sample from Tank 51 nor did it simulate all of the Tank Farm washing and decanting operations. Instead, SRNL prepared a Tank 51 SB7b sample from samples of Tank 7 and Tank 51, along with a wash solution to adjust the supernatant composition to the final SB7b Tank 51 Tank Farm projections. SRNL then prepared a sample to represent SB7b in Tank 40 by combining portions of the SRNL-prepared Tank 51 SB7b sample and a Tank 40 Sludge Batch 7a (SB7a) sample. The blended sample was 71% Tank 40 (SB7a) and 29% Tank 7/Tank 51 on an insoluble solids basis. This sample is referred to as the SB7b Qualification Sample. The blend represented the highest projected Tank 40 heel (as of May 25, 2011), and thus, the highest projected noble metals content for SB7b. Characterization was performed on the Tank 51 SB7b samples and SRNL performed DWPF simulations using the Tank 40 SB7b material. This report documents: (1) The preparation and characterization of the Tank 51 SB7b and Tank 40 SB7b samples. (2) The performance of a DWPF Chemical Process Cell (CPC) simulation using the SB7b Tank 40 sample. The simulation included a Sludge Receipt and Adjustment Tank (SRAT) cycle, where acid was added to the sludge to destroy nitrite and reduce mercury, and a Slurry Mix Evaporator (SME) cycle, where glass frit was added to the sludge in preparation for vitrification. The SME cycle also included replication of five canister decontamination additions and concentrations. Processing parameters were based on work with a nonradioactive simulant. (3) Vitrification of a portion of the SME product and characterization and durability testing (as measured by the Product Consistency Test (PCT)) of the resulting glass. (4) Rheology measurements of the SRAT receipt, SRAT product, and SME product. This program was controlled by a Task Technical and Quality Assurance Plan (TTQAP), and analyses were guided by an Analytical Study Plan. This work is Technical Baseline Research and Development (R&D) for the DWPF. It should be noted that much of the data in this document has been published in interoffice memoranda. The intent of this technical report is bring all of the SB7b related data together in a single permanent record and to discuss the overall aspects of SB7b processing.

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Analysis of DWPF Sludge Batch 6 (Macrobatch 7): Pour Stream Glass Samples

The Defense Waste Processing Facility (DWPF) began processing Sludge Batch 6 (SB6), also referred to as Macrobatch 7 (MB7), in June 2010. SB6 is a blend of the heel of Tank 40 from Sludge Batch 5 (SB5), H-Canyon Np transfers and SB6 that was transferred to Tank 40 from Tank 51.1 SB6 was processed using Frit 418. Sludge is received into the DWPF Chemical Processing Cell (CPC) and is processed through the Sludge Receipt and Adjustment Tank (SRAT) and Slurry Mix Evaporator Tank (SME). The treated sludge slurry is then transferred to the Melter Feed Tank (MFT) and fed to the melter. During processing of each sludge batch, the DWPF is required to take at least one glass sample to meet the objectives of the Glass Product Control Program (GPCP) and to complete the necessary Production Records so that the final glass product may be disposed of at a Federal Repository. The DWPF requested various analyses of radioactive glass samples obtained from the melter pour stream during processing of SB6 as well as reduction/oxidation (REDOX) analysis of MFT samples to determine the impact of Argon bubbling. Sample analysis followed the Task Technical and Quality Assurance Plan (TTQAP) and an Analytical Study Plan (ASP). Four Pour Stream (PS) glass samples and two MFT slurry samples were delivered to the Savannah River National Laboratory (SRNL) from the DWPF. Table 1-1 lists the sample information for each pour stream glass sample. SB6 PS3 (S03472) was selected as the official pour stream sample for SB6 and full analysis was requested. This report details the visual observations of the as-received SB6 PS No.3 glass sample as well as results for the chemical composition, Product Consistency Test (PCT), radionuclide content, noble metals, and glass density. REDOX results will be provided for all four pour stream samples and vitrified samples of MFT-558 and MFT-568A. Where appropriate, data from other pour stream samples will be provided.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

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.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

The Impact Of The MCU Life Extension Solvent On Sludge Batch 8 Projected Operating Windows

As a part of the Actinide Removal Process (ARP)/Modular Caustic Side Solvent Extraction Unit (MCU) Life Extension Project, a next generation solvent (NGS) and a new strip acid will be deployed. The strip acid will be changed from dilute nitric acid to dilute boric acid (0.01 M). Because of these changes, experimental testing or evaluations with the next generation solvent are required to determine the impact of these changes (if any) to Chemical Process Cell (CPC) activities, glass formulation strategies, and melter operations at the Defense Waste Processing Facility (DWPF). The introduction of the dilute (0.01 M) boric acid stream into the DWPF flowsheet has a potential impact on glass formulation and frit development efforts since B 2 O 3 is a major oxide in frits developed for DWPF. Prior knowledge of this stream can be accounted for during frit development efforts but that was not the case for Sludge Batch 8 (SB8). Frit 803 has already been recommended and procured for SB8 processing; altering the frit to account for the incoming boron from the strip effluent (SE) is not an option for SB8. Therefore, the operational robustness of Frit 803 to the introduction of SE including its compositional tolerances (i.e., up to 0.0125M boric acid) is of interest and was the focus of this study. The primary question to be addressed in the current study was: What is the impact (if any) on the projected operating windows for the Frit 803 - SB8 flowsheet to additions of B 2 O 3 from the SE in the Sludge Receipt and Adjustment Tank (SRAT)? More specifically, will Frit 803 be robust to the potential compositional changes occurring in the SRAT due to sludge variation, varying additions of ARP and/or the introduction of SE by providing access to waste loadings (WLs) of interest to DWPF? The Measurement Acceptability Region (MAR) results indicate there is very little, if any, impact on the projected operating windows for the Frit 803 - SB8 system regardless of the presence or absence of ARP and SE (up to 2 wt% B 2 O 3 contained in the SRAT and up to 2000 gallons of ARP). It should be noted that 0.95 wt% B 2 O 3 is the nominal projected concentration in the SRAT based on a 0.0125M boric acid flowsheet with 70,000 liters of SE being added to the SRAT.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

The Impact Of The MCU Life Extension Solvent On Sludge Batch 8 Projected Operating Windows

As a part of the Actinide Removal Process (ARP)/Modular Caustic Side Solvent Extraction Unit (MCU) Life Extension Project, a next generation solvent (NGS) and a new strip acid will be deployed. The strip acid will be changed from dilute nitric acid to dilute boric acid (0.01 M). Because of these changes, experimental testing or evaluations with the next generation solvent are required to determine the impact of these changes (if any) to Chemical Process Cell (CPC) activities, glass formulation strategies, and melter operations at the Defense Waste Processing Facility (DWPF). The introduction of the dilute (0.01M) boric acid stream into the DWPF flowsheet has a potential impact on glass formulation and frit development efforts since B2O3 is a major oxide in frits developed for DWPF.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Corrosion impact of reductant on DWPF and downstream facilities

Glycolic acid is being evaluated as an alternate reductant in the preparation of high level waste for the Defense Waste Processing Facility (DWPF) at the Savannah River Site (SRS). During processing, the glycolic acid is not completely consumed and small quantities of the glycolate anion are carried forward to other high level waste (HLW) facilities. The impact of the glycolate anion on the corrosion of the materials of construction throughout the waste processing system has not been previously evaluated. A literature review had revealed that corrosion data in glycolate-bearing solution applicable to SRS systems were not available. Therefore, testing was recommended to evaluate the materials of construction of vessels, piping and components within DWPF and downstream facilities. The testing, conducted in non-radioactive simulants, consisted of both accelerated tests (electrochemical and hot-wall) with coupons in laboratory vessels and prototypical tests with coupons immersed in scale-up and mock-up test systems. Eight waste or process streams were identified in which the glycolate anion might impact the performance of the materials of construction. These streams were 70% glycolic acid (DWPF feed vessels and piping), SRAT/SME supernate (Chemical Processing Cell (CPC) vessels and piping), DWPF acidic recycle (DWPF condenser and recycle tanks and piping), basic concentrated recycle (HLW tanks, evaporators, and transfer lines), salt processing (ARP, MCU, and Saltstone tanks and piping), boric acid (MCU separators), and dilute waste (HLW evaporator condensate tanks and transfer line and ETF components). For each stream, high temperature limits and worst-case glycolate concentrations were identified for performing the recommended tests. Test solution chemistries were generally based on analytical results of actual waste samples taken from the various process facilities or of prototypical simulants produced in the laboratory. The materials of construction for most vessels, components and piping were not impacted with the presence of glycolic acid or the impact is not expected to affect the service life. However, the presence of the glycolate anion was found to affect corrosion susceptibility of some materials of construction in the DWPF and downstream facilities, especially at elevated temperatures. The following table summarizes the results of the electrochemical and hot wall testing and indicates expected performance in service with the glycolate anion present.

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DWPF nitric-glycolic flowsheet chemical process cell chemistry. Part 1

The conversions of nitrite to nitrate, the destruction of glycolate, and the conversion of glycolate to formate and oxalate were modeled for the Nitric-Glycolic flowsheet using data from Chemical Process Cell (CPC) simulant runs conducted by SRNL from 2011 to 2015. The goal of this work was to develop empirical correlations for these variables versus measureable variables from the chemical process so that these quantities could be predicted a-priori from the sludge composition and measurable processing variables. The need for these predictions arises from the need to predict the REDuction/OXidation (REDOX) state of the glass from the Defense Waste Processing Facility (DWPF) melter. This report summarizes the initial work on these correlations based on the aforementioned data. Further refinement of the models as additional data is collected is recommended.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Nitric-glycolic flowsheet testing for maximum hydrogen generation rate

The Defense Waste Processing Facility (DWPF) at the Savannah River Site is developing for implementation a flowsheet with a new reductant to replace formic acid. Glycolic acid has been tested over the past several years and found to effectively replace the function of formic acid in the DWPF chemical process. The nitric-glycolic flowsheet reduces mercury, significantly lowers the chemical generation of hydrogen and ammonia, allows purge reduction in the Sludge Receipt and Adjustment Tank (SRAT), stabilizes the pH and chemistry in the SRAT and the Slurry Mix Evaporator (SME), allows for effective adjustment of the SRAT/SME rheology, and is favorable with respect to melter flammability. The objective of this work was to perform DWPF Chemical Process Cell (CPC) testing at conditions that would bound the catalytic hydrogen production for the nitric-glycolic flowsheet.

08 HYDROGEN↗

Scanning Mobility Particle Sizer (SMPS) Instrument Handbook

The Model 3936 Scanning Mobility Particle Spectrometer (SMPS) measures the size distribution of aerosols ranging from 10 nm up to 1000 nm. The SMPS uses a bipolar aerosol charger to keep particles within a known charge distribution. Charged particles are classified according to their electrical mobility, using a long-column differential mobility analyzer (DMA). Particle concentration is measured with a condensation particle counter (CPC). The SMPS is well-suited for applications including: nanoparticle research, atmospheric aerosol studies, pollution studies, smog chamber evaluations, engine exhaust and combustion studies, materials synthesis, filter efficiency testing, nucleation/condensation studies, and rapidly changing aerosol systems.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Corrosion Testing of Monofrax K-3 Refractory in Defense Waste Processing Facility (DWPF) Alternate Reductant Feeds

The Defense Waste Processing Facility (DWPF) at the Savannah River Site (SRS) uses a combination of reductants and oxidants while converting high level waste (HLW) to a borosilicate waste form. A reducing flowsheet is maintained to retain radionuclides in their reduced oxidation states which promotes their incorporation into borosilicate glass. For the last 20 years of processing, the DWPF has used formic acid as the main reductant and nitric acid as the main oxidant. During reaction in the Chemical Process Cell (CPC), formate and formic acid release measurably significant H 2 gas which requires monitoring of certain vessel’s vapor spaces. A switch to a nitric acid-glycolic acid (NG) flowsheet from the nitric-formic (NF) flowsheet is desired as the NG flowsheet releases considerably less H 2 gas upon decomposition. This would greatly simplify DWPF processing from a safety standpoint as close monitoring of the H 2 gas concentration could become less critical. In terms of the waste glass melter vapor space flammability, the switch from the NF flowsheet to the NG flowsheet showed a reduction of H 2 gas production from the vitrification process as well. Due to the positive impact of the switch to glycolic acid determined on the flammability issues, evaluation of the other impacts of glycolic acid on the facility must be examined.

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3002 Humidified Tandem Differential Mobility Analyzer (HTDMA) Instrument Handbook

The Brechtel Manufacturing Inc. (BMI) Humidified Tandem Differential Mobility Analyzer (HT-DMA Model 3002) (Brechtel and Kreidenweis 2000a,b, Henning et al. 2005, Xerxes et al. 2014) measures how aerosol particles of different initial dry sizes grow or shrink when exposed to changing relative humidity (RH) conditions. It uses two different mobility analyzers (DMA) and a humidification system to make the measurements. One DMA selects a narrow size range of dry aerosol particles, which are exposed to varying RH conditions in the humidification system. The second (humidified) DMA scans the particle size distribution output from the humidification system. Scanning a wide range of particle sizes enables the second DMA to measure changes in size or growth factor (growth factor = humidified size/dry size), due to water uptake by the particles. A Condensation Particle Counter (CPC) downstream of the second DMA counts particles as a function of selected size in order to obtain the number size distribution of particles exposed to different RH conditions.

54 ENVIRONMENTAL SCIENCES↗