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Results of Routine Strip Effluent Hold Tank and Decontaminated Salt Solution Hold Tank Samples from Modular Caustic-Side Solvent Extraction Unit during Macrobatch 5 Operations

Strip Effluent Hold Tank (SEHT) and Decontaminated Salt Solution Hold Tank (DSSHT) samples from several of the "microbatches" of Integrated Salt Disposition Project (ISDP) Salt Batch ("Macrobatch") 5 have been analyzed for 238 Pu, 90 Sr, 137 Cs, and by Inductively Coupled Plasma Emission Spectroscopy (ICPES). The results indicate good decontamination performance within process design expectations. While the data set is sparse, the results of this set and the previous set of results for Macrobatch 4 samples indicate generally consistent operations. The DSSHT samples show continued presence of titanium, likely from leaching of the monosodium titanate in the Actinide Removal process (ARP).

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Assessment of a Filtration Waste Qualification Method for LAWPS

The Low-Activity Waste Pretreatment System (LAWPS) facility is planned to pretreat Hanford tank waste supernate by filtering solids and processing through ion exchange columns to remove cesium. The filtration process is achieved through cross flow filtration using a stainless steel Mott filter with a 0.1-micron grade. The goal of this effort was to assess whether a batch, or dead end, filtration (DEF) device replicating the LAWPS cross flow filter could be employed to qualify each feed campaign prior to delivery to LAWPS. The objective for filtration feed qualification is to determine whether the cross-flow filters deployed in LAWPS will remove solids while maintaining a de minimus flow rate of permeate. To that end, the DEF was tested with simulants and the results compared with those obtained from cross flow filtration tests.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

VERSE-LC TCCR Model Calibration using Batch 1A, Batch 2, and Batch 3 Column Data

The objective of this work is to utilize on-line gamma monitoring data collected during Tank Closure Cesium Removal (TCCR) Column Batch 3 operations to calibrate the parameters (essentially, the correction/dilution factors (CF or DF)) used in the VERSE-LC models for the prediction of cesium breakthrough while processing Savannah River Site (SRS) Tank 10H dissolved saltcake High-Level Waste through a packed cylindrical bed of Crystalline Silicotitanate (CST). Calibrated VERSE-LC models could be applied to aid in evaluating future TCCR operations.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Direct Feed High-Level Waste APPS Model Glass Testing (DFHLW APPS) Matrix

This report summarizes the data collected during the batching and melting of the Direct Feed High-Level Waste APPS Model Glass Matrix (DFHLW APPS) to serve as a quality-assured validation of the Aspen Process Performance Simulation (APPS) formulation method. Of 15 glasses tested, 12 satisfied all target property constraints. Two glasses, APPS-05 and -06, formed nepheline on canister centerline cooling heat-treatment and failed the Product Consistency Test response limits. Glass APPS-07-2 formed unacceptably high concentrations of crystals (primarily Na3Nd(PO4)2) when heat treated at 950 °C. All other glasses were found to be satisfactory. The measured property values were compared to predicted values from a set of current models. In many cases the current models were found to be inadequate for design of DFHLW glasses. These models are being adjusted to correct for mispredictions. Other models, e.g., density, toxicity characteristic leaching procedure, and sulfur solubility, are adequate for formulation of DFHLW glasses.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Single instruction multiple data page table walk scheduling at input output memory management unit

A data processing system includes a memory and an input output memory management unit that is connected to the memory. The input output memory management unit is adapted to receive batches of address translation requests. The input output memory management unit has instructions that identify, from among the batches of address translation requests, a later batch having a lower number of memory access requests than an earlier batch, and selectively schedules access to a page table walker for each address translation request of a batch.

Basu, Arkaprava↗

Separation of Transmutation - and Fission-Produced Radioisotopes from Irradiated Beryllium

The primary objective of this study was to test the effectiveness of a two-step solvent extraction-precipitation process for separating transmutation and fission products from irradiated beryllium. Beryllium metal was dissolved in nitric and fluoroboric acids. Isotopes of 241Am, 239Pu, 85Sr, 60Co, and 137Cs were then added to make a surrogate beryllium waste solution. A series of batch contacts was performed with the spiked simulant using chlorinated cobalt dicarbollide and polyethylene glycol diluted with sulfone to extract the isotopes of Cs and Sr. Another series of batch contacts was performed using a combination of octyl (phenyl)-N,Ndiisobutylcarbamoylmethylphosphine oxide in tributyl phosphate diluted with dodecane for extracting the isotopes of Pu and Am. The 60Co was separated by first forming a cobalt complex and then selectively precipitating the beryllium as a hydroxide. The results indicate that greater than 99.9% removal can be achieved for each radionuclide. Transuranic isotope contamination levels are reduced to less than 100 nCi/g, and sources of high beta-gamma radiation (60Co, 137Cs, and 90Sr) are reduced to levels that will allow the beryllium to be contact handled. The separation process may be applicable to a recycle or waste disposition scenario.

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PERFORMANCE TESTING OF THE NEXT-GENERATION CSSX SOLVENT WITH ACTUAL SRS TANK WASTE

Efforts are underway to qualify the Next-Generation Solvent for the Caustic Side Solvent Extraction (CSSX) process. Researchers at multiple national laboratories have been involved in this effort. As part of the effort to qualify the solvent extraction system at the Savannah River Site (SRS), SRNL performed a number of tests at various scales. First, SRNL completed a series of batch equilibrium, or Extraction-Scrub-Strip (ESS), tests. These tests used {approx}30 mL of Next-Generation Solvent and either actual SRS tank waste, or waste simulant solutions. The results from these cesium mass transfer tests were used to predict solvent behavior under a number of conditions. At a larger scale, SRNL assembled 12 stages of 2-cm (diameter) centrifugal contactors. This rack of contactors is structurally similar to one tested in 2001 during the demonstration of the baseline CSSX process. Assembly and mechanical testing found no issues. SRNL performed a nonradiological test using 35 L of cesium-spiked caustic waste simulant and 39 L of actual tank waste. Test results are discussed; particularly those related to the effectiveness of extraction.

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Data for High Yield Production of 3-Hydroxypropionic Acid Using Issatchenkia orientalis

Biomanufacturing provides a more sustainable alternative to fossil-based chemical manufacturing. 3-Hydroxypropionic acid (3HP) is a top Department of Energy value-added chemical and precursor to bioplastics, yet cost-effective microbial production remains elusive. Here, we establish the acid-tolerant yeast Issatchenkia orientalis as a robust host for low-pH 3HP biosynthesis. Genome-scale modeling identifies the β-alanine pathway as optimal, offering the highest theoretical yield and lowest oxygen requirement. Thermodynamic analysis confirms its favorability under acidic conditions. Using sequence similarity network analysis, we discover highly active aspartate 1-decarboxylase (PAND), β-alanine-pyruvate aminotransferase (BAPAT), and 3HP dehydrogenase (YDFG), which significantly improve the pathway efficiency. Next, to further elevate the production, pathway optimization through multi-copy PAND integration, byproduct elimination (knockouts of pyruvate decarboxylase and glycerol-3-phosphate dehydrogenase), and reinforcement of aspartate flux by overexpression of pyruvate carboxylase and aspartate amino transferase improves the titer to 29 g/L in shake flasks. Fed-batch fermentation at pH 4 with low-cost corn steep liquor medium further increases the production to 92 g/L with 0.7 g/g yield and 0.55 g/L/h productivity. Techno-economic analysis indicates that such performance could potentially enable a financially viable process for sustainable acrylic acid production. This work establishes I. orientalis as a next-generation platform for cost-effective 3HP production and paves the way toward industrial commercialization.

Bioproducts↗

Roll-to-Roll Solution-Processible Small-Molecule OLEDs

The objective of this program is to develop key knowledge and make critical connections between technologies needed to enable low-cost manufacturing of OLED lighting products. In particular, the program was intended to demonstrate the feasibility of making high performance Small-Molecule OLEDs (SM-OLED) using a roll-to-roll (R2R) wet-coating technique by addressing the following technical risks (1) Whether the wet-coating technique can provide high performance OLEDs, (2) Whether SM-OLED can be made in a R2R manner, (3) What are the requirements for coating equipment, and (4) Whether R2R OLEDs can have the same performance as the lab controls. The program has been managed and executed according to the Program Management Plan (PMP) that was first developed at the beginning of the program and further revised accordingly as the program progressed. Significant progress and risk reductions have been accomplished by the end of the program. Specific achievements include: (1) Demonstrated that wet-coating can provide OLEDs with high LPW and long lifetime; (2) Demonstrated R2R OLEDs can be as efficient as batch controls (Figure 1) (3) Developed & validated basic designs for key equipment necessary for R2R SM-OLEDs; (4) Developed know-hows & specifications on materials & ink formulations critical to wet-coating; (5) Developed key R2R processes for each OLED layer (6) Identified key materials and components such as flexible barrier substrates necessary for R2R OLEDs.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Geochemical and Geomechanical Effects on Wellbore Cement Fractures

Experimental studies were conducted using batch reactors, X-ray microtomograpy (XMT), and computational fluid dynamics (CFD) simulation to determine changes in cement fracture surfaces, fluid flow pathways, and permeability with geochemical and geomechanical processes. Composite Portland cement-basalt caprock core with artificial fractures was prepared and reacted with CO2-saturated groundwater at 50°C and 10 MPa for 3 to 3.5 months under static conditions to understand the geochemical and geomechanical effects on the integrity of wellbores containing defects. Cement-basalt interface samples were subjected to mechanical stress at 2.7 MPa before the CO2 reaction. XMT provided three-dimensional (3-D) visualization of the opening and interconnection of cement fractures due to mechanical stress. After the CO2 reaction, XMT images revealed that calcium carbonate precipitation occurred extensively within the fractures in the cement matrix, but only partially along fractures located at the cement-basalt interface. The permeability calculated based on CFD simulation was in agreement with the experimentally measured permeability. The experimental results imply that the wellbore cement with fractures is likely to be healed during exposure to CO2-saturated groundwater under static conditions, whereas fractures along the cement-caprock interface are still likely to remain vulnerable to the leakage of CO2. CFD simulation for the flow of different fluids (CO2-saturated brine and supercritical CO2) using a pressure difference of 20 kPa and 200 kPa along ~2 cm-long cement fractures showed that a pressure gradient increase resulted in an increase of CO2 fluids flux by a factor of only ~3-9 because the friction of CO2 fluids on cement fracture surfaces increased with higher flow rate as well. At the same pressure gradient, the simulated flow rate was higher for supercritical CO2 than CO2-saturated brine by a factor of only ~2-3, because the viscosity of supercritical CO2 is much lower than that of CO2-saturated brine. The study suggests that in deep geological reservoirs the geochemical and geomechanical processes have coupled effects on the wellbore cement fracture evolution and fluid flow along the fracture surfaces.

36 MATERIALS SCIENCE↗

Environmental Impacts of Reclaimed Asphalt Pavement on Leaching of Metals into Groundwater

To investigate the environmental impacts of reclaimed asphalt pavement (RAP) while it was freshly processed (i.e. hot mixed asphalt or HMA) and after being subjected to weathering, three RAP materials, namely north-RAP, central-RAP, south-RAP, from three plants and one fresh HMA loose mix sample (Fresh-HMA) throughout New Jersey, USA underwent four different weathering processes including: Ultraviolet (UV) and precipitation weathering on unbounded RAP, UV and precipitation weathering on compacted RAP, weathering by heat and moisture cycles, and groundwater flow-through leaching. Batch experiments were conducted to mimic releasing of trace elements in weak acidic leachate from landfills. North-RAP and central-RAP released levels of Pb greater than the United States Environmental Protection Agency (USEPA) primary drinking water maximum contaminant level (MCL) of 15 µg/L. Novel two-column experiments (a RAP column followed by a soil column) were conducted to investigate the release of trace elements from RAP and the attenuation effect of soil on potential pollutants. The results of these experiments showed that pollutants released from RAPs such as Mn and Ni were largely attenuated in the soil. The results suggest that RAP can be used as an unbound material in environments except those acidic (i.e., pH < 5 as in mines with sulfur-containing minerals and landfills with acidic environment).

batch extraction↗

Machine Learning Algorithms for Automated NIF Capsule Mandrel Selection

Small shells, approximately 2 mm in diameter, made from Poly(α-methylstyrene) (PAMS) are used as mandrels in the production of glow discharge polymer capsules located at the center of inertial confinement fusion experiments. The visual inspection process of microscope images of these shell mandrels, including detection of micron-sized defects on the shell surface as well as the handling and sorting, is a very labor-intensive, repetitive, and highly subjective process that stands to benefit greatly from automation. As part of an effort to decrease the number of labor hours spent in capsule handling, inspection, and metrology, the development of robotic systems was presented in a paper by Carlson et al., “Automation in Target Fabrication” [Fusion Sci. Technol., Vol. 70, p. 274 (2016)]. The current work expands the automated image acquisition systems developed previously and adds the use of convolutional neural networks to select capsules best suited for use in the downstream production process. Through the use of these machine learning algorithms, the selection process becomes robust, repeatable, and operator independent. Finally, as an added benefit the system developed as part of this work is able to provide defect statistics on entire shell batches and feed this information upstream to the production team.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Potential application of curium neutron detection in the high reliability safeguards approach for remotely handled nuclear facilities

The study presented in this paper is part of a series of quantitative modeling efforts to characterize the neutron flux for the major subsystems in a pyroprocessing facility. An MCNPX model has established the electroreduction process, in which uranium oxide is converted into a metal product by electrochemical methods. This process is important because the electroreduction stage is the earliest point in the system where a diversion attempt could occur. This paper will present neutron flux for a commercial batch size. The intent of this study is to determine if the magnitude of the flux is sufficiently high as to affect facility design. (author)

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

SPECTROSCOPIC ONLINE MONITORING FOR PROCESS CONTROL AND SAFEGUARDING OF RADIOCHEMICAL STREAMS

There is a renewed interest worldwide to promote the use of nuclear power and close the nuclear fuel cycle. The long term successful use of nuclear power is critically dependent upon adequate and safe processing and disposition of the used nuclear fuel. Liquid-liquid extraction is a separation technique commonly employed for the processing of the dissolved used nuclear fuel. The instrumentation used to monitor these processes must be robust, require little or no maintenance, and be able to withstand harsh environments such as high radiation fields and aggressive chemical matrices. This paper summarizes application of the absorption and vibrational spectroscopic techniques supplemented by physicochemical measurements for radiochemical process monitoring. In this context, our team experimentally assessed the potential of Raman and spectrophotometric techniques for online real-time monitoring of the U(VI)/nitrate ion/nitric acid and Pu(IV)/Np(V)/Nd(III), respectively, in solutions relevant to spent fuel reprocessing. These techniques demonstrate robust performance in the repetitive batch measurements of each analyte in a wide concentration range using simulant and commercial dissolved spent fuel solutions. Spectroscopic measurements served as training sets for the multivariate data analysis to obtain partial least squares predictive models, which were validated using on-line centrifugal contactor extraction tests. Satisfactory prediction of the analytes concentrations in these preliminary experiments warrants further development of the spectroscopy-based methods for radiochemical process control and safeguarding. Additionally, the ability to identify material intentionally diverted from a liquid-liquid extraction contactor system was successfully tested using on-line process monitoring as a means to detect the amount of material diverted. A chemical diversion and detection from a liquid-liquid extraction scheme was demonstrated using a centrifugal contactor system operating with the simulant PUREX extraction system of Nd(NO3)3/nitric acid aqueous phase and TBP/n-dodecane organic phase. During a continuous extraction experiment, a portion of the feed from a counter-current extraction system was diverted while the spectroscopic on-line process monitoring system was simultaneously measuring the feed, raffinate and organic products streams. The amount observed to be diverted by on-line spectroscopic process monitoring was in excellent agreement with values based from the known mass of sample directly taken (diverted) from system feed solution.

fuel reprocessing↗

Spectroscopic online monitoring for process control and safeguarding of radiochemical streams

This paper summarizes application of the absorption and vibrational spectroscopic techniques supplemented by physicochemical measurements for radiochemical process monitoring. In this context, our team experimentally assessed the potential of Raman and spectrophotometric techniques for online real-time monitoring of the U(VI)/nitrate ion/nitric acid and Pu(IV)/Np(V)/Nd(III), respectively, in solutions relevant to spent fuel reprocessing. These techniques demonstrate robust performance in the repetitive batch measurements of each analyte in a wide concentration range using simulant and commercial dissolved spent fuel solutions. Spectroscopic measurements served as training sets for the multivariate data analysis to obtain partial least squares predictive models, which were validated using on-line centrifugal contactor extraction tests. Satisfactory prediction of the analytes concentrations in these preliminary experiments warrants further development of the spectroscopy-based methods for radiochemical process control and safeguarding. Additionally, the ability to identify material intentionally diverted from a liquid-liquid extraction contactor system was successfully tested using on-line process monitoring as a means to detect the amount of material diverted. (authors)

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Uptake and speciation of trace metal inputs to Wetland Soils from Illinois and South Carolina and Stream Sediments from Tennessee

Metals occur in all ecosystems, although their concentrations vary depending on their natural geologic conditions and surrounding human activities. In addition to metals intrinsically present from the geology of a particular system, metals can enter environmental systems from a wide variety of natural and anthropogenic sources, such as sediment re-suspension, mining operations, industrial processes, agricultural activities, and atmospheric deposition. While metals can be toxic at high concentrations, some metals serve as essential micronutrients for biogeochemical processes. Metal transport and availability in engineered and natural water systems depend on processes of adsorption/desorption, oxidation/reduction, dissolution/precipitation, and ligand complexation. Insights into the speciation of metals and their bioavailability will also help advance understanding of the roles of metals in the biogeochemical cycling of nutrients. We conducted batch experiments under anoxic conditions on soils and sediments collected from three different natural aquatic systems to understand their response to influxes of dissolved Cu, Ni and Zn. While soils and sediments from all sites could strongly bind added trace metals, there were substantial differences in trace metal uptake trends between different sites, especially for Cu. There was no distinct correlation between trace metal uptake and the total organic matter, iron, and sulfur content present in the samples. X-ray absorption spectroscopy indicated that the speciation of the freshly added metals taken up by the solids differs substantially from the speciation of the metals originally present in unamended samples. Cu sulfides dominated speciation at low loadings (1 µmol/g), whereas complexation to thiol groups and formation of metallic Cu governed speciation at high loadings (10 µmol/g). For Ni and Zn, adsorption to mineral surfaces and organic matter governed their speciation in materials from most sites. This study suggests that the background speciation of metals in natural aquatic systems is a poor predictor of the speciation and lability of metals introduced to terrestrial aquatic systems from anthropogenic or natural processes. Our findings imply that geochemical processes controlling trace metal speciation may vary considerably with metal loading in different natural systems. Data are provided for marsh wetland soils at Argonne National Laboratory (Marsh 1 and Marsh 2), riparian wetland soils (Riparian 1 and Riparian 2) in the Tims Branch watershed at Savannah River National Laboratory, and stream bed sediments (Stream 1 and Stream 2) from East Fork Poplar Creek near Oak Ridge National Laboratory. Data package includes the results of trace metal uptake experiments conducted on the selected sites for determining their capacity to immobilize metals under different loadings. XANES spectra for Cu, Ni, ad Zn at different loadings are included in the package. The abundance of different trace metal species obtained using linear combination fitting in ATHENA are also included in the data.

54 ENVIRONMENTAL SCIENCES↗

Adiabatic Capture and Debunching

In the study of beam preparation for the g-2 experiment, adiabatic debunching and adiabatic capture are revisited. The voltage programs for these adiabbatic processes are derived and their properties discussed. Comparison is made with some other form of adiabatic capture program. The muon g-2 experiment at Fermilab calls for intense proton bunches for the creation of muons. A booster batch of 84 bunches is injected into the Recycler Ring, where it is debunched and captured into 4 intense bunches with the 2.5-MHz rf. The experiment requires short bunches with total width less than 100 ns. The transport line from the Recycler to the muon-production target has a low momentum aperture of ~ ±22 MeV. Thus each of the 4 intense proton bunches required to have an emittance less than ~ 3.46 eVs. The incoming booster bunches have total emittance ~ 8.4 eVs, or each one with an emittance ~ 0.1 eVs. However, there is always emittance increase when the 84 booster bunches are debunched. There will be even larger emittance increase during adiabatic capture into the buckets of the 2.5-MHz rf. In addition, the incoming booster bunches may have emittances larger than 0.1 eVs. In this article, we will concentrate on the analysis of the adiabatic capture process with the intention of preserving the beam emittance as much as possible. At this moment, beam preparation experiment is being performed at the Main Injector. Since the Main Injector and the Recycler Ring have roughly the same lattice properties, we are referring to adiabatic capture in the Main Injector instead in our discussions.

43 PARTICLE ACCELERATORS↗

The Building and Commissioning of the Batch Pyrolysis Plant in Studsvik, Sweden - 12447

After a sequence of lab scale and bench scale trials the building of a pyrolysis plant could begin at the Studsvik site in Sweden. The facility is primarily aimed at treatment of uranium contaminated organic waste originating at fuel manufacturing plants and other facilities where the main contamination is uranium. The plant is an extension/addition to the already operating incinerator. In order to further widen the waste acceptance criteria the design of the off-gas treatment system does not have the same design as that of the incinerator. The building of the facility began in April 2011, and the first heating of the facility took place in late December, 2011. The site acceptance tests are planned for January, as are the first inactive trials aimed at optimisation of process control. The facility is planned to be operating with radioactive materials from February 2012. The pyrolysis unit is primarily aimed at treatment of uranium contaminated waste, under conditions that facilitate leaching and recovery of the uranium from the ashes. However, a number of other uses are conceivable. The batch fed pyrolysis unit, with its chosen design of the off-gas treatment system, enables treatment of some waste fractions that are difficult to treat in the incinerator. For instance small campaigns, i.e. smaller quantities of waste (typically <5 tonnes), or waste containing high levels of chlorine and sulphur are possible to treat in the pyrolysis unit. The pyrolysis unit is also expected to perform well in the treatment of other 'difficult' waste fractions, for instance waste containing pyrophoric materials, or other types of waste that benefit from the high level of process control, i.e. control of temperature and atmosphere throughout the process, that can be obtained in the pyrolysis unit compared to the incinerator. Furthermore, treatment in the pyrolysis unit minimises the risk of cross contamination between different waste treatment campaigns. This feature is obtained thanks to the low gas flow rates in the vessel, which means that a higher retention of nuclides in the ashes is obtained, but also through a design that facilitates cleaning of the pyrolysis vessel and the system beyond this, or even exchanging the most critical components, such as the pyrolysis vessel itself, if need be. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗