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At least 253 records · Page 14

SNS Sample Activation Calculator Experimental Validation - Paper 79

The Spallation Neutron Source (SNS) at Oak Ridge National Laboratory (ORNL) uses the Sample Activation Calculator (SAC) to calculate the activation of all samples after they have been exposed to the neutron beam in any of the neutron scattering instruments at the SNS beamlines. The SAC web page takes user inputs (choice of beamline, the mass, composition and area of the sample, irradiation time, decay time, etc.) and then calculates the activation for the sample. In recent years, the SAC has been incorporated into the user proposal and sample handling process, and beamline scientists and users have noticed discrepancies in the predicted activation of their samples. As a part of the Neutronics Analysis Group at SNS, we were tasked with validating the SAC tool and diagnosing the origin of the discrepancies seen by the beamline scientists and the users. In the process of performing these measurements, we additionally found that several aspects of realistic neutron scattering operations, and thus sample exposure, cannot be captured with current configuration of the SAC tool. Typical neutron scattering samples are irradiated for multiple periods with different neutron energy ranges; the realities of accelerator operation indicate that not all of those periods will be at the same accelerator power, and scattering samples are frequently not fully illuminated by the well-collimated neutron beam. Finally, we will explore whether neutron beams, as modified by neutron guide systems with energy-dependent intensity modifications and by precise energy-band defining mechanical choppers, are suitably analyzed with multigroup cross section libraries in which there are typically very few energy groups below one eV. (authors)

43 PARTICLE ACCELERATORS↗

Complex interactions between day length and diurnal patterns of gene expression drive photoperiodic responses in a perennial C 4 grass

Abstract Photoperiod is a key environmental cue affecting flowering and biomass traits in plants. Key components of the photoperiodic flowering pathway have been identified in many species, but surprisingly few studies have globally examined the diurnal rhythm of gene expression with changes in day length. Using a cost‐effective 3′‐Tag RNA sequencing strategy, we characterize 9,010 photoperiod responsive genes with strict statistical testing across a diurnal time series in the C 4 perennial grass, Panicum hallii . We show that the vast majority of photoperiod responses are driven by complex interactions between day length and sampling periods. A fine‐scale contrast analysis at each sampling time revealed a detailed picture of the temporal reprogramming of cis ‐regulatory elements and biological processes under short‐ and long‐day conditions. Phase shift analysis reveals quantitative variation among genes with photoperiod‐dependent diurnal patterns. In addition, we identify three photoperiod enriched transcription factor families with key genes involved in photoperiod flowering regulatory networks. Finally, coexpression networks analysis of GIGANTEA homolog predicted 1,668 potential coincidence partners, including five well‐known GI‐interacting proteins. Our results not only provide a resource for understanding the mechanisms of photoperiod regulation in perennial grasses but also lay a foundation to increase biomass yield in biofuel crops.

Weng, Xiaoyu↗

Method Validation Summary for L16.2 AD-ISO-0015 for ISO-17025 / NFAC Applications

Methods for the analysis of semi-volatile organic compounds are employed at Savannah River National Laboratory (SRNL) for routine and non-routine samples from tank waste, process control, waste acceptance, and a wide array of other process and research samples. A method has been developed by SRNL, based on existing methods for semi-volatile analysis, for the analysis of nitroaromatic high explosives by gas chromatography / mass spectrometry in soils and sediments. Relative to past work performed at SRNL on nitroaromatic explosives, this developed, optimized, and validated method can achieve lower limits of detection and quantitation, greater precision, lower bias, higher linearity, and accuracy across a greater linear range.

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Data sharing report characterization of the surveillance and maintenance project miscellaneous process inventory waste items Oak Ridge National Laboratory, Oak Ridge, TN

The U.S. Department of Energy (DOE) Oak Ridge Office of Environmental Management (EM-OR) requested Oak Ridge Associated Universities (ORAU), working under the Oak Ridge Institute for Science and Education (ORISE) contract, to provide technical and independent waste management planning support under the American Recovery and Reinvestment Act (ARRA). Specifically, DOE EM-OR requested ORAU to plan and implement a sampling and analysis campaign to target certain items associated with URS|CH2M Oak Ridge, LLC (UCOR) surveillance and maintenance (S&M) process inventory waste. Eight populations of historical and reoccurring S&M waste at the Oak Ridge National Laboratory (ORNL) have been identified in the Waste Handling Plan for Surveillance and Maintenance Activities at the Oak Ridge National Laboratory, DOE/OR/01-2565&D2 (WHP) (DOE 2012) for evaluation and processing for final disposal. This waste was generated during processing, surveillance, and maintenance activities associated with the facilities identified in the process knowledge (PK) provided in Appendix A. A list of items for sampling and analysis were generated from a subset of materials identified in the WHP populations (POPs) 4, 5, 6, 7, and 8, plus a small number of items not explicitly addressed by the WHP. Specifically, UCOR S&M project personnel identified 62 miscellaneous waste items that would require some level of evaluation to identify the appropriate pathway for disposal. These items are highly diverse, relative to origin; composition; physical description; contamination level; data requirements; and the presumed treatment, storage, and disposal facility (TSDF). Because of this diversity, ORAU developed a structured approach to address item-specific data requirements necessary for acceptance in a presumed TSDF that includes the Environmental Management Waste Management Facility (EMWMF)—using the approved Waste Lot (WL) 108.1 profile—the Y-12 Sanitary Landfill (SLF) if appropriate; EnergySolutions Clive; and the Nevada National Security Site (NNSS) (ORAU 2013b). Finally, the evaluation of these wastes was more suited to a judgmental sampling approach rather than a statistical design, meaning data were collected for each individual item, thereby providing information for item-byitem disposition decisions. ORAU prepared a sampling and analysis plan (SAP) that outlined data collection strategies, methodologies, and analytical guidelines and requirements necessary for characterizing targeted items (ORAU 2013b). The SAP described an approach to collect samples that allowed evaluation as to whether or not the waste would be eligible for disposal at the EMWMF. If the waste was determined not to be eligible for EMWMF disposal, then there would be adequate information collected that would allow the waste to be profiled for one of the alternate TSDFs listed above.

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Progress in Uranium Chemistry: Driving Advances in Front-End Nuclear Fuel Cycle Forensics

The front-end of the nuclear fuel cycle encompasses several chemical and physical processes used to acquire and prepare uranium for use in a nuclear reactor. These same processes can also be used for weapons or nefarious purposes, necessitating the need for technical means to help detect, investigate, and prevent the nefarious use of nuclear material and nuclear fuel cycle technology. Over the past decade, a significant research effort has investigated uranium compounds associated with the front-end of the nuclear fuel cycle, including uranium ore concentrates (UOCs), UF 4 , UF 6 , and UO 2 F 2 . These efforts have furthered uranium chemistry with an aim to expand and improve the field of nuclear forensics. Focus has been given to the morphology of various uranium compounds, trace elemental and chemical impurities in process samples of uranium compounds, the degradation of uranium compounds, particularly under environmental conditions, and the development of improved or new techniques for analysis of uranium compounds. Overall, this research effort has identified relevant chemical and physical characteristics of uranium compounds that can be used to help discern the origin, process history, and postproduction history for a sample of uranium material. This effort has also identified analytical techniques that could be brought to bear for nuclear forensics purposes. Continued research into these uranium compounds should yield additional relevant chemical and physical characteristics and analytical approaches to further advance front-end nuclear fuel cycle forensics capabilities.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Design of an ultrahigh vacuum transfer mechanism to interconnect an oxide molecular beam epitaxy growth chamber and an x-ray photoemission spectroscopy analysis system

We designed a mechanism and the accompanying sample holders to transfer between a VEECO 930 oxide molecular beam epitaxy (MBE) and a PHI Versa Probe X-ray photoemission spectroscopy (XPS) chamber within a multiple station growth, processing, and analysis system through ultrahigh vacuum (UHV). The mechanism consists of four parts: (1) a platen compatible with the MBE growth stage, (2) a platen compatible with the XPS analysis stage, (3) a sample coupon that is transferred between the two platens, and (4) the accompanying UHV transfer line. The mechanism offers a robust design that enables transfer back and forth between the growth chamber and the analysis chamber, and yet is flexible enough to allow transfer between standard sample holders for thin film growth and masked sample holders for making electrical contacts and Schottky junctions, all without breaking vacuum. We used this mechanism to transfer a barium strontium titanate thin film into the XPS analysis chamber and performed XPS measurements before and after exposing the sample to the air. After air exposure, a thin overlayer of carbon was found to form and a significant shift ({approx}1 eV) in the core level binding energies was observed.

36 MATERIALS SCIENCE↗

Radiocarbon analysis of soil microbial biomass via direct chloroform extraction

Microbial processing of soil organic matter is a significant driver of C cycling, yet we lack an understanding of what shapes the turnover of this large terrestrial pool. In part, this is due to limited options for accurately identifying the source of C assimilated by microbial communities. Laboratory incubations are the most common method for this; however, they can introduce artifacts due to sample disruption and processing and can take months to produce sufficient CO 2 for analysis. We present a biomass extraction method which allows for the direct 14 C analysis of microbial biomolecules and compare the results to laboratory incubations. In the upper 50 cm soil depths, the Δ 14 C from incubations was indistinguishable from that of extracted microbial biomass. Below 50 cm, the Δ 14 C of the biomass was more depleted than that of the incubations, either due to the stimulation of labile C decomposition in the incubations, the inclusion of biomolecules from non-living cells in the biomass extractions, or differences in C used for assimilation versus respiration. Our results suggest that measurement of Δ 14 C of microbial biomass extracts can be a useful alternative to soil incubations.

54 ENVIRONMENTAL SCIENCES↗

Performance assessment modeling of a generic SNF/HLW repository in salt with coupled thermal-hydrologic effects - 15423

This paper describes advances in performance assessment modeling of deep geologic repositories facilitated by a massively parallel, high-performance computing (HPC) environment. Our new Generic Disposal System Analysis (GDSA) Framework utilizes the massively parallel PFLOTRAN multi-physics code to simulate repository performance in the presence of coupled thermal-hydrologic-chemical processes, linked to DAKOTA, an HPC uncertainty sampling and propagation code that provides nested parallelism for multi-realization performance assessment and sensitivity analysis. This enhanced performance assessment (PA) modeling capability is demonstrated with deterministic and probabilistic simulations of a generic repository for SNF and HLW in bedded salt host rock, by comparing repository performance between a case with heat-generating waste ('thermal' case) and a case without heat generation ('isothermal' case). The simulation results provide preliminary insights into the effect of multi-physics processes and thermal-hydrologic coupling on the long-term behavior of a reference-case salt repository. (authors)

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Omics-Lethal Human Viruses, West Nile Experiment WCN002

The purpose of this experiment was to evaluate the host response to wild-type West Nile virus (WNV NY99 clone 382) and mutant (WNVE218A) virus infection. Sample data was obtained from mouse cortical neuron tissue and processed for mRNA and miRNA expression analysis. This data set comprises two complete biological replicate experiments conducted in the same conditions and with data processed independently (WCN003). Secondary host-associated viral dataset downloads contain one or more statistically processed (normalization data transformation) quantitative dataset collections resulting in qualitative expression analyses of primary host-pathogen experimental study designs. Transcriptomics dataset downloads have a direct relationship to a primary sample submission corresponding to a specific West Nile virus infection.

59 BASIC BIOLOGICAL SCIENCES↗

Application of Generic Disposal System Models

This report describes specific GDSA activities in fiscal year 2015 (FY2015) toward the development of the enhanced disposal system modeling and analysis capability for geologic disposal of nuclear waste. The GDSA framework employs the PFLOTRAN thermal-hydrologic-chemical multi-physics code (Hammond et al., 2011) and the Dakota uncertainty sampling and propagation code (Adams et al., 2013). Each code is designed for massively-parallel processing in a high-performance computing (HPC) environment. Multi-physics representations in PFLOTRAN are used to simulate various coupled processes including heat flow, fluid flow, waste dissolution, radionuclide release, radionuclide decay and ingrowth, precipitation and dissolution of secondary phases, and radionuclide transport through the engineered barriers and natural geologic barriers to a well location in an overlying or underlying aquifer. Dakota is used to generate sets of representative realizations and to analyze parameter sensitivity.

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Recovery of Rare Earth Elements from Coal and Coal Byproducts via a Closed Loop Leaching Process: Final Report

Objectives: Through this grant, Battelle proposes to address Area of Interest (AOI) 1 to develop a bench-scale technology to economically separate, extract, and concentrate mixed REEs from coal ash. U.S. coal and coal byproducts provide the opportunity for a domestic source of REEs. The DOE’s National Energy Technology Laboratory (NETL) has characterized various coal and coal byproducts samples and has found varying concentrations of REE ranging up to 1,000 parts per million by weight. The primary project objective is to validate the economic viability of recovering REEs from the coal byproduct coal ash using Battelle’s patented closed-loop Acid Digestion Process (ADP). This will be accomplished by selecting coal sources with the potential to provide REE concentrations above 300 parts per million by weight, collecting characterization data for coal ash samples generated via three different methods, and performing a Techno-Economic Analysis (TEA) for the proposed process. The regional availability of REE-laden coal ash, the regional market for rare earth concentrates, and the system capital and operating costs for rare earth recovery using the ADP technology will be accounted for in the TEA. Limited laboratory testing will be conducted to generate the parameters needed for the design of a bench scale system for REE recovery. The ultimate project outcome will be the design for an optimized, closed loop process to economically recovery REEs such that the process may be demonstrated at the bench scale in a Phase 2 project. Project Description: The project will encompass evaluation of the ADP technology for the economic recovery of REEs from coal and coal ash. The ADP was originally designed and demonstrated for the U.S. Army to facilitate demilitarization of cast-cured munitions via acid digestion in a closed-loop process. Proof of concept testing has been conducted on a sample of Ohio-based Middle Kittanning coal and has demonstrated the feasibility of recovering REEs using the ADP technology. In AOI 1, Ohio coal sources with the potential to provide a consistent source of rare earth element concentrations above 300 parts per million will be identified. Coal sample inventories from West Virginia and Pennsylvania will also be assessed for purposes of comparison. Three methods of preparing the coal ash will be evaluated for their potential to enhance the technical feasibility and economics of REE recovery. Three sources of coal ash are targeted for evaluation of the economics of REE recovery in this project: (1) coal ash from power generation stations, to include fly ash and/or bottom ash, (2) ash generated in a lower temperature ashing process, and (3) ash residual from Battelle’s coal liquefaction process. Making use of residual ash from coal liquefaction processes directly leverages work currently being conducted by Battelle for DOE NETL in response to DE-FOA-0000981 entitled “Greenhouse Gas Emissions Reductions Research and Development Leading to Cost-Competitive Coal-to-Liquids Based Jet Fuel Production.” Using the sample characterization results and regional information regarding REE concentration, availability and cost, a TEA will be developed. The previously generated laboratory testing results for leaching and REE recovery via the ADP will be used to perform the TEA, along with common engineering assumptions for scale up of equipment and labor costs. Finally, upon validation of the economic feasibility of the process by the TEA, limited laboratory testing will be performed to support the design of a bench scale system. In a future project phase, it is envisioned that the bench scale system will be constructed and operated to prove the process on a continuous basis.

20 FOSSIL-FUELED POWER PLANTS↗

Studies of QCD structure in high-energy collisions

”Studies of QCD structure in high-energy collisions” is a research project in theoretical particle physics at Southern Methodist University funded by US DOE Award DE-SC0013681. The award furnished bridge funding for one year (2015/04/15-2016/03/31) between the periods funded by Nadolsky’s DOE Early Career Research Award DE-SC0003870 (in 2010-2015) and a DOE grant DE-SC0010129 for SMU Department of Physics (starting in April 2016). The primary objective of the research is to provide theoretical predictions for Run-2 of the CERN Large Hadron Collider (LHC). The LHC physics program relies on state-of-the-art predictions in the field of quantum chromodynamics. The main effort of our group went into the global analysis of parton distribution functions (PDFs) employed by the bulk of LHC computations. Parton distributions describe internal structure of protons during ultrarelivistic collisions. A new generation of CTEQ parton distribution functions (PDFs), CT14, was released in summer 2015 and quickly adopted by the HEP community. The new CT14 parametrizations of PDFs were obtained using benchmarked NNLO calculations and latest data from LHC and Tevatron experiments. The group developed advanced methods for the PDF analysis and estimation of uncertainties in LHC predictions associated with the PDFs. We invented and refined a new ’meta-parametrization’ technique that streamlines usage of PDFs in Higgs boson production and other numerous LHC processes, by combining PDFs from various groups using multivariate stochastic sampling. In 2015, the PDF4LHC working group recommended to LHC experimental collaborations to use ’meta-parametrizations’ as a standard technique for computing PDF uncertainties. Finally, to include new QCD processes into the global fits, our group worked on several (N)NNLO calculations.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Metabolome patterns identify active dechlorination in bioaugmentation consortium SDC-9™

Ultra-high performance liquid chromatography–high-resolution mass spectrometry (UPHLC–HRMS) is used to discover and monitor single or sets of biomarkers informing about metabolic processes of interest. The technique can detect 1000’s of molecules (i.e., metabolites) in a single instrument run and provide a measurement of the global metabolome, which could be a fingerprint of activity. Despite the power of this approach, technical challenges have hindered the effective use of metabolomics to interrogate microbial communities implicated in the removal of priority contaminants. Herein, our efforts to circumvent these challenges and apply this emerging systems biology technique to microbiomes relevant for contaminant biodegradation will be discussed. Chlorinated ethenes impact many contaminated sites, and detoxification can be achieved by organohalide-respiring bacteria, a process currently assessed by quantitative gene-centric tools (e.g., quantitative PCR). This laboratory study monitored the metabolome of the SDC-9™ bioaugmentation consortium during cis-1,2-dichloroethene (cDCE) conversion to vinyl chloride (VC) and nontoxic ethene. Untargeted metabolomics using an UHPLC-Orbitrap mass spectrometer and performed on SDC-9™ cultures at different stages of the reductive dechlorination process detected ~10,000 spectral features per sample arising from water-soluble molecules with both known and unknown structures. Multivariate statistical techniques including partial least squares-discriminate analysis (PLSDA) identified patterns of measurable spectral features (peak patterns) that correlated with dechlorination (in)activity, and ANOVA analyses identified 18 potential biomarkers for this process. Statistical clustering of samples with these 18 features identified dechlorination activity more reliably than clustering of samples based only on chlorinated ethene concentration and Dhc 16S rRNA gene abundance data, highlighting the potential value of metabolomic workflows as an innovative site assessment and bioremediation monitoring tool.

environmental monitoring↗

Microfluidic sorting of protein nanocrystals by size for X-ray free-electron laser diffraction

The advent and application of the X-ray free-electron laser (XFEL) has uncovered the structures of proteins that could not previously be solved using traditional crystallography. While this new technology is powerful, optimization of the process is still needed to improve data quality and analysis efficiency. One area is sample heterogeneity, where variations in crystal size (among other factors) lead to the requirement of large data sets (and thus 10–100 mg of protein) for determining accurate structure factors. To decrease sample dispersity, we developed a high-throughput microfluidic sorter operating on the principle of dielectrophoresis, whereby polydisperse particles can be transported into various fluid streams for size fractionation. Using this microsorter, we isolated several milliliters of photosystem I nanocrystal fractions ranging from 200 to 600 nm in size as characterized by dynamic light scattering, nanoparticle tracking, and electron microscopy. Sorted nanocrystals were delivered in a liquid jet via the gas dynamic virtual nozzle into the path of the XFEL at the Linac Coherent Light Source. We obtained diffraction to ∼4 Å resolution, indicating that the small crystals were not damaged by the sorting process. We also observed the shape transforms of photosystem I nanocrystals, demonstrating that our device can optimize data collection for the shape transform-based phasing method. Using simulations, we show that narrow crystal size distributions can significantly improve merged data quality in serial crystallography. From this proof-of-concept work, we expect that the automated size-sorting of protein crystals will become an important step for sample production by reducing the amount of protein needed for a high quality final structure and the development of novel phasing methods that exploit inter-Bragg reflection intensities or use variations in beam intensity for radiation damage-induced phasing. This method will also permit an analysis of the dependence of crystal quality on crystal size.

36 MATERIALS SCIENCE↗

Thermal Activation of Zirconium(IV) Acetylacetonate Catalysts to Enhance Polyurethane Synthesis and Reprocessing

Carbamate formation and exchange catalysts enable efficient polyurethane (PU) manufacturing, as well as emerging recycling and reprocessing methods for PU thermosets. Zirconium β-diketonate complexes, such as Zr acetylacetonate [Zr(acac) 4 ], are effective alternatives to toxic organotin catalysts that have been used for PU reprocessing. Here, we report that Zr(acac) 4 undergoes a thermally activated process in the PU network during reprocessing that transforms it into a more active carbamate exchange catalyst. This process is associated with the irreversible loss of acetylacetonate ligands and is not observed for the more sterically hindered Zr 2,2,6,6-tetramethyl-3,5-heptanedione [Zr(tmhd) 4 ] complex. Crossover experiments between PU thermoplastics indicated enhanced carbamate exchange after the thermal activation of Zr(acac) 4 in the presence of one of the PUs, whereas a sample of Zr(acac) 4 activated in the absence of the PU had no catalytic activity. Thermal gravimetric analysis suggested that this process is associated with the loss of one protonated acac ligand. Stress relaxation analysis of PU thermosets indicated a distinct change in the characteristic relaxation time associated with the thermal activation of Zr(acac) 4 at temperatures above 140 °C; no such change was observed for samples reprocessed using Zr(tmhd) 4 . Density functional theory and molecular experiments suggest that irreversible ligand exchange of acac with alkoxide or carbamate reduces the activation energy for urethane formation and reversion. Furthermore, the Zr(acac) 4 catalyst activated in the presence of a PU’s polyol precursor provided more porous and less dense PU foams compared to those made using the unactivated Zr(acac) 4 catalyst. Furthermore, these findings are important for developing improved PU synthesis and recycling processes. Thermally activating a catalyst during reprocessing may provide more nuanced control of the in-use and reprocessing characteristics of PU thermosets.

Alcohols↗

A hybrid data–model approach to map soil thickness in mountain hillslopes

Abstract. Soil thickness plays a central role in the interactions between vegetation, soils, and topography, where it controls the retention and release of water, carbon, nitrogen, and metals. However, mapping soil thickness, here defined as the mobile regolith layer, at high spatial resolution remains challenging. Here, we develop a hybrid model that combines a process-based model and empirical relationships to estimate the spatial heterogeneity of soil thickness with fine spatial resolution (0.5 m). We apply this model to two aspects of hillslopes (southwest- and northeast-facing, respectively) in the East River watershed in Colorado. Two independent measurement methods – auger and cone penetrometer – are used to sample soil thickness at 78 locations to calibrate the local value of unconstrained parameters within the hybrid model. Sensitivity analysis using the hybrid model reveals that the diffusion coefficient used in hillslope diffusion modeling has the largest sensitivity among all input parameters. In addition, our results from both sampling and modeling show that, in general, the northeast-facing hillslope has a deeper soil layer than the southwest-facing hillslope. By comparing the soil thickness estimated between a machine-learning approach and this hybrid model, the hybrid model provides higher accuracy and requires less sampling data. Modeling results further reveal that the southwest-facing hillslope has a slightly faster surface soil erosion rate and soil production rate than the northeast-facing hillslope, which suggests that the relatively less dense vegetation cover and drier surface soils on the southwest-facing slopes influence soil properties. With seven parameters in total for calibration, this hybrid model can provide a realistic soil thickness map with a relatively small amount of sampling dataset comparing to machine-learning approach. Integrating process-based modeling and statistical analysis not only provides a thorough understanding of the fundamental mechanisms for soil thickness prediction but also integrates the strengths of both statistical approaches and process-based modeling approaches.

58 GEOSCIENCES↗

Analysis of Harrell Monosodium Titanate Lot #46000908120

Monosodium titanate (MST) for use in the Actinide Removal Process (ARP) must be qualified and verified in advance. A single qualification sample for each batch of material is sent to SRNL for analysis, as well as a statistical sampling of verification samples. The Harrell Industries Lot #46000908120 qualification and the 16 verification samples failed to meet the specification for weight percent solids. All of the pails sampled and tested contained less than 15 wt % MST solids.

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Analysis of Harrell Monosodium Titanate Lot #46000824120

Monosodium titanate (MST) for use in the Actinide Removal Process (ARP) must be qualified and verified in advance. A single qualification sample for each batch of material is sent to SRNL for analysis, as well as a statistical sampling of verification samples. The Harrell Industries Lot #46000824120 qualification and the 16 verification samples failed to meet the specification for weight percent solids. All of the pails sampled and tested contained less than 15 wt % MST solids.

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