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At least 739 records · Page 41

Utilization and Application of Kurion Mobile Processing System in Remediation of Radioactively Contaminated Water - 16370

Kurion{sup R} Mobile Processing Systems (KMPS) were deployed in Fukushima as first-of-a- kind at-tank isotope removal systems to remediate Sr from reverse osmosis concentrated salt water. The systems were successful in their efforts and achieved their decontamination and availability goals. The use of KMPS has been considered for other applications where a modular system is of benefit. The use of different Kurion Ion Specific Media (ISM) allows for precision removal of hazardous ions from a variety of waste streams. This paper describes a range of projects in which KMPS modularity will benefit the nuclear industry. The KMPS is a flexible system that can be deployed quickly and efficiently. One treatment system option being considered is the utilization of a KMPS for the removal of contamination from groundwater. Similar to its use in Japan, the KMPS can be sent to remote locations for the direct treatment of ground water. In particular, there are several sites across the world where uranium contamination is a problem. Uranium treatability testing was performed on collected groundwater samples from a radiologically contaminated site. The tests were used to help provide designs for KMPS modifications. These designs included the addition of chemical treatment module for the control of pH and other chemistry, the addition of an ultraviolet module for the destruction of biological material, among others. The tests determined the loading capacities of uranium capture resins (UCR) and media (UCM) for this specific waste stream. Based on uranium loading capacities of 37.3 mg/L (end of test C/C{sub 0} = 0.5) and 54.6 mg/L (extrapolated to C/C{sub 0} = 0.98), and the longevity of the resin (45,911 BV for C/C{sub 0} = 0.5, and 80,556 BV for C/C{sub 0} = 0.98) UCR-1 was selected as the media/resin to be proposed for a uranium treatment system. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Quality Control Algorithms for the Kennedy Space Center 50-Megahertz Doppler Radar Wind Profiler Winds Database

This paper presents the process used by the Marshall Space Flight Center Natural Environments Branch (EV44) to quality control (QC) data from the Kennedy Space Center's 50-MHz Doppler Radar Wind Profiler for use in vehicle wind loads and steering commands. The database has been built to mitigate limitations of using the currently archived databases from weather balloons. The DRWP database contains wind measurements from approximately 2.7-18.6 km altitude at roughly five minute intervals for the August 1997 to December 2009 period of record, and the extensive QC process was designed to remove spurious data from various forms of atmospheric and non-atmospheric artifacts. The QC process is largely based on DRWP literature, but two new algorithms have been developed to remove data contaminated by convection and excessive first guess propagations from the Median Filter First Guess Algorithm. In addition to describing the automated and manual QC process in detail, this paper describes the extent of the data retained. Roughly 58% of all possible wind observations exist in the database, with approximately 100 times as many complete profile sets existing relative to the EV44 balloon databases. This increased sample of near-continuous wind profile measurements may help increase launch availability by reducing the uncertainty of wind changes during launch countdown

Barbre, Robert E., Jr.↗

GrayQb Single-Faced Version 2 Open Environment Test - 16344

The GrayQb{sup TM} Single Faced Version 2 (SF2) is a non-destructive examination device developed to generate radiation contour maps showing source locations and relative radiological levels present in an area under examination. This device allows for characterization of radioactively contaminated areas such as hot cells, gloveboxes, small and large rooms, hallways, and waste tanks. The goal of GrayQb{sup TM} (pronounced 'Gray Cube') is to provide a low cost easily deployable device to aid in the process of decontamination and decommissioning (D and D). The GrayQb{sup TM} SF2 device is approximately a six inch cube weighing seven (7) pounds composed of a tungsten shield with integrated collimator, radiation imaging medium (Phosphor Storage Plate), and digital camera. This paper details the design upgrades incorporated into the new version of the GrayQb{sup TM} SF2 device and the characterization testing of this upgraded device. Device results from controlled testing performed at the Savannah River Site (SRS) Health Physics Instrument Calibration Laboratory (HPICL) are presented, as well as results from the open environment field testing performed in the E-Area Low Level Waste Storage Area. Follow on work performed deploying the GrayQb SF2 device at the Hanford Plutonium Reclamation Facility (PRF) to assist in the radiological characterization of the canyon will also be presented. Testing of the redesigned GrayQb{sup TM} SF2 device demonstrated its ability to detect low energy isotopes, e.g. Am-241 and Pu-238, not only indoors in controlled environments with well-defined source locations, but also in open environment field areas with a significant high energy background. Additionally, it was demonstrated that the device could detect higher energy isotopes (Cs-137 and Co-60) in a controlled setting and with additional testing and/or modifications to device and software, would likely be able to detect these isotopes in the open environment field testing. Follow on 2015 work performed at Hanford proved GrayQb to be a useful tool in the radiological characterization of the PRF canyon. Distribution tendencies of the radiological hot spots were identified that provided insights which will assist in more efficient planning of the continued D and D effort. Hot spots were identified which can be targeted during the future D and D effort and used as markers during the NDA assessment to quantify the radiological environment. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

FX2 advanced fogging technology - 15711

Problem statement: The need for an advanced technology that can better address potential airborne contaminants at DOE Savannah River Site 235-F. Current methods of knocking down or fixing this contamination are labor intensive, costly, and sometimes ineffective. Thus, to make exposure ALARA, the advanced fogging effort is being tested using Idaho National Laboratory's FX2 fixative agent. The FX2 fogging agent is a proprietary mixture of water, latex paint (LTX), glycerin (GLY) and sodium lauryl sulfate (SLS). Initial development began in 2006 when a DOE Small Business Innovative Research (SBIR) grant resulted in the development of a conceptual advanced capture coating fog system. This coating is shown to be excellent at reducing airborne contamination and 'fixing' particulates in place as demonstrated by Idaho National Lab. Controlling Potential Airborne Particulates: Testing capacity to knockdown airborne particulates. Evaluating ability to fix to different surfaces (e.g., glass, wood, steel, concrete, brick). Line of sight as well as non-line of sight (shadowed) locations will be tested for coverage. Adhesiveness and Coverage of Surface Area: Contact area will be placed under air pressure to attempt dislodging of dried mixture. Particle analysis utilizing ImageJ will be conducted to determine quantifiable coverage. Ignitability: Observation of the FX2's reactivity to flame and heat sources as it is being applied. Results will provide useful information for the prevention of potential hazards. Determine Shielding Properties Against Alpha Sources: Determine the shielding abilities of the FX2. Fogging agent against an alpha particle emitting point source. Evaluating Critical Properties: These properties will be evaluated to better characterize the FX2 and allow for optimal understanding of results: ASTM E1354 - Burn Rate; NFPA 296-Flashover; ASTM D2196 - Viscosity; ASTM D1331 - Surface Tension; ASTM D792 - Density. Testing Innovations: Developed by the National Institutes of Health, ImageJ is a public domain image processing program that allows for the analysis that this effort requires. Coverage: Through contrast analysis, ImageJ can be used to determine the coverage of the agent upon any of the testing surfaces. Correlations: With the feature of coverage evaluation, a relationship, and thus a graphical representation, can be made between surface coverage and radiation shielding. Future work: Engineering and manufacturing of mobile robotic fogging device. ASTM WK5394: establishing performance specifications for stabilizers to minimize migration of dispersible radioactive contamination.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

The effects of Fe-oxidizing microorganisms on post-biostimulation permeability reduction and oxidative processes at the Rifle IFRC site

Fe oxidation and biomineral formation is important in aquifers because the highly-reactive oxides can control the mobility of nutrients (e.g. phosphate, C) and metals (e.g. arsenic, uranium). Mineral formation also has the potential to affect hydrology, depending on the volume and distribution in pore spaces. In this exploratory study, we sought to understand how microbial Fe-oxidizers and their biominerals affect, and are affected by groundwater flow. As part of work at the Rifle aquifer in Colorado, we initially hypothesized that Fe-oxidizers were contributing to aquifer clogging problems associated with enhanced bioremediation. To demonstrate the presence of Fe-oxidizers in the Rifle aquifer, we enriched FeOM from groundwater samples, and isolated two novel chemolithotrophic, microaerophilic Fe-oxidizing Betaproteobacteria, Hydrogenophaga sp. P101 and Curvibacter sp. CD03. To image cells and biominerals in the context of pores, we developed a “micro-aquifer,” a sand-filled flow-through culture chamber that allows for imaging of sediment pore space with multiphoton confocal microscopy. Fe oxide biofilms formed on sand grains, demonstrating that FeOM produce Fe oxide sand coatings. Fe coatings are common on aquifer sands, and tend to sequester contaminants; however, it has never previously been shown that microbes are responsible for their formation. In contrast to our original hypothesis, the biominerals did not clog the mini-aquifer. Instead, Fe biofilm distribution was dynamic: they grew as coatings, then periodically sloughed off sand grains, with some flocs later caught in pore throats. This has implications for physical hydrology, including pore scale architecture, and element transport. The sloughing of coatings likely prevents the biominerals from clogging wells and aquifers, at least initially. Although attached biomineral coatings sequester Fe-associated elements (e.g. P, As, C, U), when biominerals detach, these elements are transported as particles through the aquifer. Our work shows that microbial mineralization impacts in aquifers are dynamic, and that the fate and transport of biomineral-associated elements depend not only on geochemical conditions, but also physical pore-scale processes.

54 ENVIRONMENTAL SCIENCES↗

High-Resolution Three-Dimensional Sculpting of Two-Dimensional Graphene Oxide by E-Beam Direct Write

On demand switchable additive/subtractive patterning of 2D nanomaterials is an essential capability for developing new concepts of functional nanomaterials and their device realizations. Traditionally, this is performed via a multi-step process using photoresist coating and patterning by conventional photo or electron beam lithography, which is followed by bulk dry/wet etch or deposition. This limits the range of functionalities and structural topologies that can be achieved, as well as increases the complexity, cost, and possibility of contamination which are significant barriers to device fabrication from highly sensitive 2D materials. Focused electron beam induced processing (FEBIP) enables a material chemistry/site-specific, high-resolution multi-mode atomic scale processing and provides unprecedented opportunities for direct-write, single-step surface patterning of 2D nanomaterials with an in-situ imaging capability. It allows for realizing a rapid multi-scale/multi-mode approach, ranging from an atomic scale manipulation (e.g., via targeted defect introduction as an active site) to a large-area surface modification on nano and micro scales, including patterned doping and material removal/deposition with 2D (in-plane)/3D (out-of-plane) control. In this work, we report on a new capability of FEBIP for nanoscale patterning of graphene oxide via removal of oxygenated carbon moieties with no use of reactive gas required for etching complemented by carbon atom deposition using focused electron beam. The mechanism of experimentally observed phenomena is explored using the density functional theory (DFT) calculations, revealing that interactions of e-beam liberated reactive oxygen radicals with carbon atoms on graphene basal plane lead to creation of atomic vacancies in the material. The reaction by-products are volatile carbon di-oxides, which are dissociated and volatilized from the graphene oxide surface functional groups by interactions with an energetic focused electron beam. Along with selective “subtractive” patterning of graphene oxide, the same electron beam with increased irradiation doses can deposit out-of-plane 3D carbon nanostructures on top of or around the 2D etched pattern, thus forming a hybrid 2D/3D nanocomposite with feature control down to a few nanometers. Furthermore, this in-operando dual nanofabrication capability of FEBIP is unmatched by any other nanopatterning techniques and opens a new design window for forming 2D/3D complex nanostructures and functional nanodevices.

36 MATERIALS SCIENCE↗

The Development of Catalysts for Upgrading of Pyrolysis Vapor for Refinery Feedstocks and Intermediates (CRADA Final Report)

Catalytic fast pyrolysis (CFP) is a versatile technology platform to convert biomass into fungible hydrocarbon transportation fuels and chemical co-products. Key technical barriers to reaching this goal include increasing the product yields and achieving the desired fuel properties for gasoline, diesel, and jet range fuels or blendstocks that would be suitable for introduction into existing refinery unit operations. Overcoming these barriers will require durable catalysts that are effective at upgrading and stabilizing biomass pyrolysis vapors. Towards these goals, this CRADA leveraged NREL experience as a leader in biomass pyrolysis research and Johnson Matthey's (JM) experience as a leader in the production of advanced catalytic materials. The scope spanned CFP catalyst development, characterization, multi-scale reaction testing, and computational modeling. CRADA benefits to DOE, Participant, and U.S. Taxpayer: Assists laboratory in achieving programmatic scope, Uses the laboratory’s core competencies. The purpose of this CRADA was to develop and deploy catalysts for biomass CFP to help achieve cost-competitive biofuels and bio-based products. This was accomplished through a close collaboration between biomass conversion researchers at NREL and catalyst development researchers at JM. Summary of Research Results: Focus Area 1. Foundational research on catalytic conversion and deactivation: Key interactions between pyrolysis vapors and heterogeneous catalysts were probed through catalyst characterization, model compound reaction testing, and atomistic-scale computational modeling. Catalyst development focused on multifunctional materials, which include zeolites, oxides, carbides, and nitrides. Computational modeling identified reaction mechanisms and elucidated surface chemistry to test hypotheses regarding mechanisms of deoxygenation, coupling, cracking, dehydration, coke formation, hydrogen transfer, and aromatic ring reactions. This information was used to design multifunctional catalysts to increase product yields, control product selectivity, and reduce deactivation during CFP and downstream processing steps. The results served to increase fundamental understanding of key catalyst attributes and durability features for the upgrading of biomass pyrolysis vapors. Model compound experiments confirmed the importance of metal-acid bifunctionality for the deoxygenation of lignin-derived phenolic species under hydrodeoxygenation conditions. This insight led to the development of catalysts such as Pt/TiO2 and Mo2C, which were confirmed as high-performing materials during subsequent bench-scale experiments using biomass-derived pyrolysis vapors. This focus area also led to the identification of important catalyst deactivation mechanisms associated with the deposition of inorganic contaminants such as potassium. The molecular-level insight from model compound experiments and computational modeling, shown in Figure 1, informed the development of regeneration procedures that have been shown to be effective for restoration of > 90% of initial catalyst activity. This understanding has subsequently been translated to other catalyst systems, including zeolite materials that can be operated without requirements for co-fed hydrogen.

09 BIOMASS FUELS↗

Extrapolation of space weathering processes to other small solar system bodies

A diverse range of processes were invoked as the dominant factor or as important contributory factors in the modification of the optical surface and regolith of the moon. These include impact vitrification by large and small projectiles, solar wind implantation and the reduction of oxidized iron during energetic events, sputtering and crystal lattice damage by energetic cosmic rays, shock metamorphism of minerals, mixing of diverse lithologies by impacts, and contamination by external materials. These processes are also potentially important on the rocky surfaces of other small solar system bodies. For icy bodies, several additional processes are also possible, including formation of complex organic compounds from methane and ammonia-bearing ices by ultraviolet irradiation and the condensation of vapor species to form frost layers in the polar or cooler regions of objects at appropriate heliocentric distances. The lunar case, even when completely understood, will not extend in a simple linear fashion to other small rocky objects, nor will the optical surfaces of those objects all be affected to the same degree by each process. The major factors that will control the relative efficacy of a possible mechanism include the efficiency of ejecta retention and the degree to which the regolith materials experience multiple events (primarily a function of body size, escape velocity, and impactor velocities); the mean duration of typical regolith particle exposure at the optical surface and within reach of the micrometeorite, cosmic ray, solar wind, or UV fluxes (a function of the rate and scale of regolith mixing, production, and removal processes); the incident flux of solar (low energy) cosmic rays, solar wind, or UV radiation (inverse square of heliocentric distance) or of galactic (high energy) cosmic rays (slowly increasing flux with heliocentric distance); and the compositional and mineralogical nature of the surface being affected. In general, those processes that depend upon either the retention of impact ejecta or on the presence of multigenerational regoliths should be substantially less effective on smaller bodies with lower escape velocities. However, there are important exceptions to this generalization. For example, a process that involves the hypervelocity impact of small particles into a fine-grained regolith may be able to effectively retain highly shocked or melted material due to the nature of shock wave propagation in such a heterogeneous material.

Gaffey, M. J.↗

Crossflow membrane filtration system for operando fouling characterization using transmission x-ray scattering

Membrane-based separations are widely used for wastewater treatment due to their low cost and efficiency. However, membrane fouling, which is the unwanted deposition or attachment of contaminants on membrane surfaces and/or within membrane pores, remains a major challenge as it increases the mass transfer resistance and reduces membrane productivity. Membrane fouling is typically probed by macroscopic performance metrics, such as flux decline, and ex situ characterization. However, this does not capture the membrane and fouling layer evolution under operating conditions, potentially masking important mechanisms and nonequilibrium pathways that impact fouling. Here, we present a remotely controlled crossflow membrane system and a custom membrane cell for operando fouling characterization using transmission small/wide angle x-ray scattering (SAXS/WAXS). This approach allows direct observation of the nanoscale changes occurring at the membrane surface during pressurized water treatment processes, enabling a new way to understand the connections between dynamic fouling behaviors and membrane performance. Nanoparticle fouling of porous membranes during ultrafiltration was investigated using operando SAXS, and mineral scaling of reverse osmosis membranes was investigated using operando WAXS. Furthermore, this system allows for tracking membrane fouling in real time and under realistic conditions, providing fundamental physical insights into how water chemistry and operating conditions affect macroscopic membrane performance. Moreover, this system opens the door for future in situ and operando studies, and it serves as a testbed for evaluating novel materials/processes for membrane-based separations.

36 MATERIALS SCIENCE↗

Instrumentation for Examining Microbial Response to Changes In Environmental Pressures

The Automated Adaptive Directed Evolution Chamber (AADEC) is a device that allows operators to generate a micro-scale analog of real world systems that can be used to model the local-scale effects of climate change on microbial ecosystems. The AADEC uses an artificial environment to expose cultures of micro-organisms to environmental pressures, such as UV-C radiation, chemical toxins, and temperature. The AADEC autonomously exposes micro-organisms to selection pressures. This improves upon standard manual laboratory techniques: the process can take place over a longer period of time, involve more stressors, implement real-time adjustments based on the state of the population, and minimize the risk of contamination. We currently use UV-C radiation as the main selection pressure, UV-C is well studied both for its cell and DNA damaging effects as a type of selection pressure and for its related effectiveness as a mutagen; having these functions united makes it a good choice for a proof of concept. The AADEC roadmap includes expansion to different selection pressures, including heavy metal toxicity, temperature, and other forms of radiation.The AADEC uses closed-loop control to feedback the current state of the culture to the AADEC controller that modifies selection pressure intensity during experimentation, in this case culture density and growth rate. Culture density and growth rate are determined by measuring the optical density of the culture using 600 nm light. An array of 600 nm LEDs illuminate the culture and photodiodes are used to measure the shadow on the opposite side of the chamber.Previous experiments showed that we can produce a million fold increase to UV-C radiation over seven iterations. The most recent implements a microfluidic system that can expose cultures to multiple different selection pressures, perform non-survival based selection, and autonomously perform hundreds of exposure cycles. A scalable pump system gives the ability to pump in various different growth media to individual cultures and introduce chemical toxins during experimentation; AADEC can perform freeze and thaw cycles. We improved our baseline characterization by building a custom UV-C exposure hood, a shutter operates on a preset timer allowing the user to set exposure intensity consistently for multiple iterations.

Environment↗

Status of Electronics Upgrades to the LANL Green is Clean Phoswich Detector Systems - 16419

Los Alamos National Laboratory radiological facilities produce low-density room trash that, in many cases, is not contaminated with radioactivity. It has been estimated that 50 to 90% of low-density room trash is free of radioactive contamination and eligible for inclusion in LANL's Green is Clean (GIC) program. The GIC program is a verification program for non-regulated waste from radiation controlled areas that has been actively segregated as nonradioactive through the use of the waste generator's acceptable knowledge. The GIC program has employed two large area Phoswich gamma ray detector systems (HERCULES and ZEUS) to assay and verify that GIC candidate waste meets free release disposal requirements. The large area (127 cm{sup 2}) Phoswich detectors consist of a thin NaI front crystal (3 mm thick) that is optically coupled to a thick CsI back crystal (50 mm thick). The crystals are set in an oxygen-free high-conductivity copper housing with a very thin (0.025 mm) aluminum entrance window. The scintillation properties of the two crystals are different enough to allow the system's electronic components to identify the origin of any pulse. The original systems utilize Nuclear Instrumentation Module (NIM) electronics to process the detector signals. These electronic modules provide the buffering, amplification, and pulse shape analyzer needed for the proper presentation of signals to the custom Phosmux router module. The router module separates the sodium iodide and cesium iodide signals by their rise times and transfers this information into the computer-mounted multichannel analyzer, a Canberra Model S-100 system. While these NIM Bin counting electronics configurations have been effective for approximately 20 years of operation, they are bulky requiring numerous modules per detector and the important Phosmux module is no longer manufactured by LANL. Modern advancement of commercial counting electronics now offer more compact options for equivalent detector signal processing. A pulse shape discriminator module, the DGF Pixie-4, made by XIA LLC, has been identified that can replace the majority of the original NIM bin electronics in a much more compact chassis - one Pixie-4 replaces four NIM amplifiers and four NIM PSAs and fits in a small National Instruments{sup TM} chassis. Thus, LANL has initiated a system upgrade project to replace the historic NIM electronics with the XIA Pixie4 and associated configuration software. The hardware for one Phoswich systems has been procured for the project and the configuration software, customized for the LANL Phoswich detector application, has been written by the manufacturer. Initial setup and optimization of the Pixie-4 configuration has been performed. Qualitative and quantitative baseline comparisons to the NIM electronics has been performed. Good agreement of key low energy gamma lines between the systems has allowed 'Proof of Concept' to be concluded. Further optimization and performance evaluations are in progress. Modifications to the LabVIEW{sup TM} based operating software (originally written by VI Control Systems Ltd.) are being performed by a LANL LabVIEW{sup TM} programmer to accommodate the electronics upgrade. A new LabVIEW{sup TM} interface to control the Pixie-4 has already been developed. Final optimization and testing, formal software QA, and revisions to operating procedures are in progress to achieve completion of the GIC system upgrade project. (authors)

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The role of nanopores on U(VI) sorption and redox behavior in U(VI)-contaminated subsurface sediments

Most reactive surfaces in clay-dominated sediments are present within nanopores (pores of nm dimension). The behavior of geological fluids and minerals in nanopores is significantly different from those in normal non-nanoporous environments. The effect of nanopore surfaces on U(VI) sorption/desorption and reduction is likely to be significant in clay-rich subsurface environments. Our research results from both model nanopore system and natural sediments from both model system (synthetic nanopore alumina) and sediments from the ORNL Field Research Center prove that U(VI) sorption on nanopore surfaces can be greatly enhanced by nanopore confinement environments. The results from the project provide advanced mechanistic, quantitative information on the physiochemical controls on uranium sorption and redox behavior in subsurface sediments. The influence of nanopore surfaces on coupled uranium sorption/desorption and reduction processes is significant in virtually all subsurface environments, because most reactive surfaces are in fact nanopore surfaces. The results will enhance transfer of our laboratory-based research to a major field research initiative where reductive uranium immobilization is being investigated. Our results will also provide the basic science for developing in-situ colloidal barrier of nanoporous alumina in support of environmental remediation and long term stewardship of DOE sites.

54 ENVIRONMENTAL SCIENCES↗

Traditional Forensic Examinations on Bulk Special Nuclear Material

The Federal Bureau of Investigation (FBI) Laboratory at Quantico, Virginia is responsible for the forensic examination of radiological evidence and evidence contaminated with radioactive materials. Due to these unique hazards and the necessary specialized safety protocols, the FBI has developed a network of Partner Laboratories (PLs) across the United States of America to support conventional forensic examinations of radiological evidence and evidence contaminated with radioactive materials. In support of this, the FBI Laboratory has established the Hazardous Evidence Analysis Team (HEAT), a group of qualified forensic examiners, scientists, technicians, and photographers who can deploy to laboratories outside of the FBI Laboratory at Quantico, VA to perform conventional forensics on evidence containing/contaminated with hazardous materials. One of the FBI’s PLs, the United States Department of Energy’s Los Alamos National Laboratory (LANL), in Los Alamos, New Mexico, has unique facilities, personnel, and procedures to secure, safely handle, and process significant quantities of special nuclear material (SNM). While LANL’s procedures for working with SNM are well established, working with SNM under evidentiary controls is not. Close cooperation between LANL and FBI HEAT is required due to FBI policies on evidence handling, as well as the challenges associated with the exploitation and preservation of conventional forensics (fingerprints, trace evidence, and photography) on SNM evidence.

98 NUCLEAR DISARMAMENT, SAFEGUARDS, AND PHYSICAL P↗

Spaceflight Effect on White Matter Structural Integrity

Recent reports of elevated brain white matter hyperintensity (WMH) counts and volume in postflight astronaut MRIs suggest that further examination of spaceflight's impact on the microstructure of brain white matter is warranted. To this end, retrospective longitudinal diffusion-weighted MRI scans obtained from 15 astronauts were evaluated. In light of the recent reports of microgravity-induced cephalad fluid shift and gray matter atrophy seen in astronauts, we applied a technique to estimate diffusion tensor imaging (DTI) metrics corrected for free water contamination. This approach enabled the analysis of white matter tissue-specific alterations that are unrelated to fluid shifts, occurring from before spaceflight to after landing. After spaceflight, decreased fractional anisotropy (FA) values were detected in an area encompassing the superior and inferior longitudinal fasciculi and the inferior fronto-occipital fasciculus. Increased radial diffusivity (RD) and decreased axial diffusivity (AD) were also detected within overlapping regions. In addition, FA values in the corticospinal tract decreased and RD measures in the precentral gyrus white matter increased from before to after flight. The results show disrupted structural connectivity of white matter in tracts involved in visuospatial processing, vestibular function, and movement control as a result of spaceflight. The findings may help us understand the structural underpinnings of the extensive spaceflight-induced sensorimotor remodeling. Prospective longitudinal assessment of the white matter integrity in astronauts is needed to characterize the evolution of white matter microstructural changes associated with spaceflight, their behavioral consequences, and the time course of recovery. Supported by a grant from the National Space Biomedical Research Institute, NASA NCC 9-58.

Lee, Jessica K.↗

In situ Infrared Spectroelectrochemistry for Understanding Structural Transformations of Precisely Defined Ions at Electrochemical Interfaces

Understanding the intrinsic properties of electroactive species at electrode-electrolyte interfaces (EEIs) is essential to the rational design of high-performance solid-state energy conversion and storage systems. In situ spectroscopy combined with cyclic voltammetry (CV) provides insights into structural changes of electroactive species at functioning EEIs. Ion soft-landing enables precisely-controlled deposition of massand charge-selected ions onto electrode surfaces thereby avoiding the contamination inherent with conventional electrode preparation techniques. In this contribution, we describe a new approach for the simultaneous electrochemical and spectroscopic characterization of soft-landed ions at operating solid-state EEIs. The technique exploits a specially-fabricated three-electrode cell that is compatible with in situ infrared reflection absorption spectroscopy (IRRAS) characterization of the softlanded ions. Keggin polyoxometalate (POM) anions, PW12O40 3-, were selected as a model system for these experiments due to their multielectron redox activity, structural stability, and well-characterized IRRAS spectrum. In situ CV measurements indicated continuous multielectron transfer processes of the soft-landed PW12O40 3- anions over a large potential range of -2.1 to -0.3 V. A distinct shift in the wavenumber of the terminal W=Ot stretching vibration in the IRRAS spectra was observed during the multielectron reduction process. The results demonstrate the capabilities of the in situ spectroelectrochemical approach for examining structural changes of well-defined electroactive species during electron transfer processes at operating solid-state EEIs.

Su, Pei↗

Load planning in the dark: RH-TRU waste container load planning at Sandia National Laboratories/New Mexico - 15116

Sandia National Laboratories (Sandia) performed several sets of experiments during the 1970's and 1980's with fresh and irradiated mixed oxide (MOX) and uranium oxide (UO{sub 2}) materials designed to simulate various fuel responses under varying reactor conditions. These research materials were from light water and breeder mixed oxide reactors. The experimental vessels and extraneous piece parts resulting from the experiments were identified as eligible for disposal at the Waste Isolation Pilot Plant (WIPP) as remote-handled (RH) transuranic (TRU) waste. Once Sandia received the approval to dispose at WIPP, discussions began with the Carlsbad Field Office (CBFO) and Nuclear Waste Partnerships, LLC (NWP) to provide Central Characterization Program (CCP) support for certified acceptable knowledge, visual examination, and dose-to-curie for the repackaging effort. In addition to the WIPP support, Sandia was required to prepare a load plan describing the configuration of the parent containers and how they could be repackaged to meet WIPP and other regulatory requirements. However, all of these containers were packaged as material twenty (20) or thirty (30) years ago and the records of the packaging process and configuration were not documented as waste. Therefore, it seemed that the load plans were prepared with limited information regarding parent container configuration, hence in the dark. The design of the Auxiliary Hot Cell Facility (AHCF) in technical area (TA) V, where the repackaging was to take place, along with the shipping requirements for the RH 72-B cask, limited the options for repackaging. This configuration required that 0.114 m{sup 3} (30-gallon) containers be packaged in the hot cell, removed and placed into 0.208 m{sup 3} (55-gallon) containers to mitigate contamination issues. The material had been tracked as accountable nuclear material and Sandia had verified Material Control and Accountability (MC and A) data on each parent container. Based on the MC and A data, scaling factors could be determined and sampling and analysis was not required. However, it meant that parent containers could not be split into two daughter containers, though two or more parent containers could be combined into one daughter. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Ion exchange selectivity in clay is controlled by nanoscale chemical–mechanical coupling

Ion exchange in nanoporous clay-rich media plays an integral role in water, nutrient, and contaminant storage and transport. In montmorillonite (MMT), a common clay mineral in soils, sediments, and muds, the swelling and collapse of clay particles through the addition or removal of discrete molecular layers of water alters cation exchange selectivities in a poorly understood way. Here, we show that ion exchange is coupled to the dynamic delamination and restacking of clay layers, which creates a feedback between the hydration state of the exchanging cation and the composition of the clay interlayer. Particles with different hydration states are distinct phases with unique binding selectivities. Surprisingly, equilibrium achieved through thermal fluctuations in cation concentration and hydration state leads to the exchange of both ions and individual MMT layers between particles, a process we image directly with high-resolution transmission electron microscopy at cryogenic conditions (cryo-TEM). We introduce an exchange model that accounts for the binding selectivities of different phases, which is likely applicable to many charged colloidal or macromolecular systems in which the structural conformation is correlated with the activities of water and counterions within spatially confined compartments.

Whittaker, Michael L.↗

Major Effects of Nonmetallic Inclusions on the Fatigue Life of Disk Superalloy Demonstrated

The fatigue properties of modern powder metallurgy disk alloys can vary because of the different steps of materials and component processing and machining. Among these variables, the effects of nonmetallic inclusions introduced during the powder atomization and handling processes have been shown to significantly degrade low-cycle fatigue life. The levels of inclusion contamination have, therefore, been reduced to less than 1 part per million in state-of-the-art nickel disk powder-processing facilities. Yet the large quantities of compressor and turbine disks weighing from 100 to over 1000 lb have enough total volume and surface area for these rare inclusions to still be present and limit fatigue life. The objective of this study was to investigate the effects on fatigue life of these inclusions, as part of the Crack Resistant Disk Materials task within the Ultra Safe Propulsion Project. Inclusions were carefully introduced at elevated levels in a nickel-base disk superalloy, U720, produced using powder metallurgy processing. Multiple strain-controlled fatigue tests were then performed on extracted test specimens at 650 C. Analyses were performed to compare the low-cycle fatigue lives and failure initiation sites as functions of inclusion content and fatigue conditions. Powder of the nickel-base superalloy U720 was atomized in argon at Special Metals Corporation, Inc., using production-scale high-cleanliness powder-processing facilities and handling practices. The powder was then passed through a 270-mesh screen. One portion of this powder was set aside for subsequent consolidation without introduced inclusions. Two other portions of this powder were seeded with alumina inclusions. Small, polycrystalline soft (Type 2) inclusions of about 50 mm diameter were carefully prepared and blended into one powder lot, and larger hard (Type 1) inclusions of about 150 mm mean diameter were introduced into the other seeded portion of powder. All three portions of powder were then sealed in separate containers, hot isostatically pressurized, extruded, forged into subscale disks, and heat treated. Low-cycle-fatigue specimens were then extracted, machined, and tested. Fatigue tests were performed at 650 C in closed-loop servohydraulic testing machines using induction heating and axial extensometers. All tests were continued to failure, and fractographic evaluations were performed on all specimens to determine the crack initiation sites. A large majority of the failures in specimens with introduced inclusions occurred at cracks initiating from inclusions at the specimen surface, as shown for each type of inclusion in the following bar chart. The inclusions significantly reduced fatigue life from unseeded material levels, as shown in the bar chart. These effects were found to depend on the strain range, strain ratio, and inclusion size. Tests at lower strain ranges and higher strain ratios resulted in larger effects of inclusions on life. Inclusion effects on life were thereby maximized in tests at the lowest strain range of 0.6 percent and the most positive strain ratio of 0.5. Under these conditions, small Type 2 inclusions reduced life substantially-- about 20 times, whereas large Type 1 inclusions dramatically reduced life 100 times. These results clearly demonstrate that it is essential to include the effects of inclusions for realistic predictions of disk fatigue life. Important issues, including temperature dependence, crack initiation versus propagation, surface treatments, realistic disk features and machining, and realistic disk spin testing will be addressed to accurately model inclusion effects on disk fatigue life. Fatigue life varied from well over 105 cycles for no inclusions to a little over 103 cycles for 100-micrometer inclusions. A single crack initiating at a surface-connected seeded inclusion caused failure in each case.

Gabb, Timothy P.↗