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At least 1,117 records · Page 62

Characterization and CST Batch Contact Equilibrium Testing of Aged TCCR Tank 10H Batch 1A and 2 Process Supernate Samples

The Tank Closure Cesium Removal (TCCR) system uses ion exchange columns filled with Crystalline Silicotitanate (CST) media to process radioactive waste solutions for the removal of Cs-137. TCCR currently focuses on dissolving Savannah River Site (SRS) Tank 10H waste (primarily sodium saltcake solids) within the tank followed by at-tank ion exchange column treatment. Previous equilibrium batch contact tests conducted in the SRNL Shielded Cells laboratory and associated analyses indicated that CST cesium removal performance was lower than predicted by ZAM modeling for TCCR Tank 10H Production Supernate Batch 1A. An average cesium distribution coefficient of 1,948 mL/g which corresponds to 94.1% Cs + removal was observed for Batch 1A supernate at 38 °C in January of 2019 using laboratory pretreated IONSIV™ R9120-B a CST from Lot #209900034 (predominant TCCR CST batch) at a phase ratio of 122 mL/g. This cesium loading was approximately 32% lower than model predictions, presumably due to ion exchange competition or fouling associated with alkaline earth or transition metals present in the solutions at low levels. The current testing was designed to: 1) evaluate whether supernate compositional changes during storage would result in improved cesium removal performance with CST, and 2) assist in media selection and handling protocols for future TCCR columns by evaluating several CST manufacturer batches as well as samples of one CST batch which had been pretreated using two different methods (field and laboratory methods).

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Panel Session 116: Waste Management from Remediation of Legacy Sites or Unplanned Releases

Past experiences have shown that there is often a disconnect between Indigenous societies and Western society. This disconnect can be attributed to different value systems between these two group and is not limited to the USA and Canada but also extends into Australia, New Zealand, and the Central Asia Republics (the 'five Stans'). The intent of this Panel Session to give voice to representatives from Indigenous communities, the challenges presented in remediation processes, and potential solutions. Standard risk assessment assumptions developed for Western societies often do not adequately address the cultural and spiritual values that may be unique to indigenous societies. This panel focused on the perspectives of Indigenous societies (e.g., Indian Tribes (US), First Nations (Canada)) related to risk assessment of environmental remediation challenges, including deep geological disposal of HLW and ILW, near-surface disposal of LLW and in-situ entombment of nuclear reactor components, and environmental remediation of abandoned uranium mines and historic wastes. Standard risk assessment assumptions often do not adequately address the cultural and spiritual values that may be unique to indigenous societies. Factoring those into a risk assessment that still meets regulatory requirements and policies such as reasonably anticipated land use at US EPA CERCLA sites can be challenging but has the potential to lead to a site or facility approach that is more accepted. Panelists with presentations: The U.S. Nuclear Regulatory Commission Regulatory Process - A Path for Indigenous Knowledge? (Francis Cameron); Local Community Perceptions and Remediation Projects (Michelle Roberts); Indigenous Perspectives on Risk Assessment (Bob Watts); Navajo Superfund Program: Fundamental Law and Traditional Ecological Knowledge (Dariel Yazzie); Risk Assessment: Two Indigenous Approaches (Whitney Fraser)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Mo/Ti Diffusion Bonding for Making Thermoelectric Devices

An all-solid-state diffusion bonding process that exploits the eutectoid reaction between molybdenum and titanium has been developed for use in fabricating thermoelectric devices based on skutterudite compounds. In essence, the process is one of heating a flat piece of pure titanium in contact with a flat piece of pure molybdenum to a temperature of about 700 C while pushing the pieces together with a slight pressure [a few psi (of the order of 10 kPa)]. The process exploits the energy of mixing of these two metals to form a strong bond between them. These two metals were selected partly because the bonds formed between them are free of brittle intermetallic phases and are mechanically and chemically stable at high temperatures. The process is a solution of the problem of bonding hot-side metallic interconnections (denoted hot shoes in thermoelectric jargon) to titanium-terminated skutterudite n and p legs during the course of fabrication of a unicouple, which is the basic unit cell of a thermoelectric device (see figure). The hot-side operating temperature required for a skutterudite thermoelectric device is 700 C. This temperature precludes the use of brazing to attach the hot shoe; because brazing compounds melt at lower temperatures, the hot shoe would become detached during operation. Moreover, the decomposition temperature of one of the skutterudite compounds is 762 C; this places an upper limit on the temperature used in bonding the hot shoe. Molybdenum was selected as the interconnection metal because the eutectoid reaction between it and the titanium at the ends of the p and n legs has characteristics that are well suited for this application. In addition to being suitable for use in the present bonding process, molybdenum has high electrical and thermal conductivity and excellent thermal stability - characteristics that are desired for hot shoes of thermoelectric devices. The process takes advantage of the chemical potential energy of mixing between molybdenum and titanium. These metals have a strong affinity for each other. They are almost completely soluble in each other and remain in the solid state at temperatures above the eutectoid temperature of 695 C. As a result, bonds formed by interdiffusion of molybdenum and titanium are mechanically stable at and well above the original bonding temperature of about 700 C. Inasmuch as the bonds are made at approximately the operating temperature, thermomechanical stresses associated with differences in thermal expansion are minimized.

Sakamoto, Jeffrey↗

CST Batch Contact Equilibrium Testing of TCCR Tank 10H Batch 1 and 1A Waste Supernate Samples

The Tank Closure Cesium Removal (TCCR) system uses ion exchange columns filled with crystalline silicotitanate media to process radioactive waste solutions for the removal of Cs-137. TCCR currently focuses on dissolving Savannah River Site (SRS) Tank 10H waste (primarily sodium saltcake solids) within the tank followed by at-tank ion exchange column treatment. Equilibrium batch contact tests conducted in the SRNL Shielded Cells laboratory and associated analyses indicated that both the Tank 10H Batch 1 (pre-production) and 1A (production) waste supernates are unique solutions for which CST cesium removal performance is lower than predicted by ZAM modeling. Cesium distribution coefficients (K d ), percent removal, and CST loading data for the TCCR production supernate batch are provided in Table ES-1. ZAM-based cesium loading predictions are compared to the observed loading for the production batch in Figure ES-1, where significantly lower performance was observed than predicted by the model. Even lower cesium loading results (versus ZAM) were observed previously for the in-tank “teabag” batch contact samples.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Brittle-to-Ductile Transitions of Polyelectrolyte Complexes: Humidity, Temperature, and Salt

Polyelectrolyte complexation is an entropically driven, associative phase separation that results in a polymer-rich polyelectrolyte complex (PEC) and a polymer-poor supernatant. PECs show promise as a new class of sustainable materials since they can be processed using aqueous solutions rather than organic solvents. Previous reports have looked at the mechanical properties and glass transitions of PECs as a function of temperature, relative humidity (rH), and salt concentration (CS), but establishing a universal understanding of how these parameters affect PEC mechanics has yet to be achieved. We examined the effects of temperature, rH, and CS on the mechanical properties of PECs formed from poly(methacrylic acid) and poly(trimethyl aminoethyl methacrylate) with a goal of establishing design rules for their mechanical response. Relative humidity was shown to have the most dramatic effect on the mechanical properties, with temperature and salt concentration having far less of an impact. Furthermore, we observed that the glass transition of PECs is tied to both temperature and relative humidity, creating a glass transition rH g /T g line that can be modulated by added salt. Finally, we looked at the thermodynamics behind the glass transition of PECs, which yielded similar energies as the condensation of water. Here, we propose the use of water and/or salt as a low energy and efficient method of processing PECs for various applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Ozonesonde Quality Assurance: JOSIE-SHADOZ (2017) and SHALLOTS (2018)

Ozonesonde data constitute a mainstay of satellite calibration and are used for climatologies and analysis of trends, especially in the lower stratosphere where satellites are most uncertain. The electrochemical-concentration cell (ECC) ozonesonde has been deployed at ~100 stations worldwide since the 1960s, with changes over time in manufacture and procedures, including details of the cell chemical solution and data processing. As a consequence, there are biases among different stations and discontinuities in profile timeseries from individual site records. Since 1996 the Jülich [Germany] Ozone Sonde Intercomparison Experiment (JOSIE) has periodically tested ozonesondes in a simulation chamber designated the World Calibration Centre for Ozonesondes by WMO. In October- November 2017 a JOSIE campaign evaluated the sondes and procedures used in SHADOZ (Southern Hemisphere Additional Ozonesondes), a 14-station tropical and subtropical network. A distinctive feature of the 2017 JOSIE was that the tests were conducted by operators from eight SHADOZ stations; Nairobi, Natal, Irene, Costa Rica, Paramaribo, Reunion, Hanoi, Kuala Lumpur. Experimental protocols and preliminary results for the SHADOZ sonde configurations, which represent most of those in use today, are described. SHADOZ stations that follow WMO-recommended protocols record total ozone within 3% of the JOSIE reference instrument. Instrument biases noted in prior JOSIE and field tests like BESOS (2004) were noted in JOSIE-2017, with maximum effect in the stratosphere. In June 2018 we organized a series of dual launches during the OWLETS II campaign in the Maryland and Chesapeake Bay area (SHALLOTS = SHADOZ-OWLETS ParaLLel Ozonesonde Test Study). Instrument and solution types were varied as in JOSIE-2017 and three radiosonde-ozonesonde variants were tested. An example of a parallel sampling in SHALLOTS, from a Greenbelt EnSCI-iMet sonde combination flown with the Wallops SPCLMS package, is illustrated in the Figure. The result was a range of biases but in general the instrument combination (EnSCI-iMet) deployed at 11 SHADOZ stations recorded ~5-10% less ozone in the stratosphere than the SPC ECC sonde flown with a Vaisala or LMS system. These 2017 and 2018 results and prior JOSIEs demonstrate that regular testing is essential to maintain best practices in ozonesonde operations and to ensure high-quality data for the ozone assessment communities.

Quality assurance↗

A history of pore water oxygen isotope evolution in the Cretaceous Travis Peak Formation in East Texas

Oxygen isotope analyses of diagenetic cements can provide detailed evidence of sedimentary burial processes and conditions, as the δ 18 O values of precipitating minerals reflect contemporaneous local δ 18 O water and temperature conditions. Uncertainties in the timing and rates of pore water δ 18 O evolution in sedimentary basins can complicate interpretation of these records. Fracture-bridging (0.5–1 mm) quartz cements observed in sandstones of the Cretaceous Travis Peak Formation in the East Texas basin show clear growth-zoning by cathodoluminescence and contain detailed fluid inclusion records of temperature that make them excellent candidates for interrogating prolonged histories of basin temperature and the evolution of δ 18 O in basin pore water. New secondary ion mass spectrometer (SIMS) δ 18 O quartz isotopic data from fluid inclusion-rich quartz bridges in Travis Peak sandstones record a steady increase of pore water δ 18 O values from ~5 to 7‰ (VSMOW; Vienna Standard Mean Ocean Water) as the sandstone warms from ~130 to 150 °C. To help evaluate whether this trend could be generated solely from local water-rock interactions in response to burial compaction, a one-dimensional closed system isotopic burial model was created to simulate how δ 18 O water values change in a quartz-dominated sandstone during diagenesis. Using both directly measured and inferred rates of Travis Peak compaction, the magnitude of change in δ 18 O water that we calculate from quartz bridge geochemistry cannot be reasonably modeled solely by local quartz mechanical compaction, pressure solution, and cementation processes, necessitating significant fluxes of silica and high-δ 18 O water from outside of the sandstones prior to maximum burial. In conclusion, this indicates that even units which appear surrounded by significant barriers to fluid flow (i.e., mudrock-bounded channel sandstones) may have been infiltrated and diagenetically modified by large fluxes of fluid on geologic time scales.

58 GEOSCIENCES↗

Cascade Distillation Subsystem Development: Early Results From the Exploration Life Support Distillation Technology Comparison Test

In 2009, the Cascade Distillation Subsystem (CDS) wastewater processor (Honeywell International, Torrance, CA) was assessed in the National Aeronautics and Space Administration (NASA) Exploration Life Support (ELS) distillation comparison test. The purpose of the test was to collect data to support down-selection and development of a primary distillation technology for application in a lunar outpost water recovery system. The CDS portion of the comparison test was conducted between May 6 and August 19, 2009. The system was challenged with two pretreated test solutions, each intended to represent a feasible wastewater generated in a surface habitat. The 30-day equivalent wastewater loading volume for a crew of four was processed for each wastewater solution. Test Solution 1 consisted of a mixed stream containing human-generated urine and humidity condensate. Test Solution 2 contained the addition of human-generated hygiene wastewater to the solution 1 waste stream components. Approximately 1500 kg of total wastewater was processed through the CDS during testing. Respective recoveries per solution were 93.4 +/- 0.7 and 90.3 +/- 0.5%. The average specific energy of the system was calculated to be less than 130 W-hr/kg. The following paper provides detailed information and data on the performance of the CDS as challenged per the ELS distillation comparison test.

Callahan, Michael R.↗

On the Conversion of Bauxite Ores to Highly Activated Alumina Media for Water Remediation

Good quality drinking water is necessary to maintain a high quality of life. Millions lack access to clean and safe drinking water, and current trends suggest that billions will face acute water shortages in the coming decades. Development of new materials has led to technological impacts on water purification, from desalination membranes to atmospheric water scavenging. However, the most challenging aspect of technological solutions is cost: if the community being serviced cannot afford the solution, it is not likely to be sustainable. Repurposing Earth-abundant materials to replace highly engineered solutions is an atractive solution. Herein, minimal processing of bauxite rocks produces a high-porosity and reactive activated alumina in situ, without purification directly from the ore. This acid-treated, thermally activated bauxite (ATAB) exhibits a high surface area of 401 ± 6 m 2 g -1 , a 40-fold increase relative to its parent ore, and a 2× increase relative to the state-of-the-art fluoride adsorbent, activated alumina. The composition, preparation, and mechanism of adsorption are studied by X-ray diffraction, X-ray photoelectron spectroscopy, and multiple-quantum magic-angle spinning 27 Al nuclear magnetic resonance (NMR). Finally, the maximum adsorption density of ATAB is comparable with that of activated alumina, but ATAB requires fewer processing steps, thus warranting future consideration as a primary adsorbent of choice for fluoride removal from water.

36 MATERIALS SCIENCE↗

Hierarchically Structured Catalysts Toward Sustainable Hydrogen Economy: Electro‐ and Thermo‐Chemical Pathways

Abstract Hydrogen, as an important clean energy source, plays a more and more crucial role in decarbonizing the planet and meeting the global climate challenge due to its high energy density and zero‐emission. The demand for sustainable hydrogen is increasing drastically worldwide as driven by the global shift towards low‐carbon energy solutions. Thermochemical catalysis process dominates hydrogen production at scale given its relatively mature technology and commercialization status, as well as the established manufacturing infrastructure. While due to its environmentally friendly nature and growing abundant sources of renewable electricity, the electrochemical path for hydrogen production is rising as a major alternative to the thermochemical means. Nevertheless, hierarchically structured catalysts and devices have gradually taken the center stage toward replacing the traditional counterparts, especially with the rapid advancement of the design and manufacture of such ordered nanostructure assemblies toward high activity, efficient mass transport, and superb stability. In this review, the latest progress of the hierarchically structured catalysts for hydrogen production have been surveyed on electro‐ and thermo‐ chemical pathways comparatively. It covers the structure designs of atomic dispersion, nanoscale surfaces and interfaces for achieving highly active and durable catalysts, components, and devices. Both electrochemical and thermochemical approaches are reviewed in terms of the vast design details, engineered benefits, and understandings of various Pt‐group metal (PGM) and non‐PGM based transition metal catalysts for hydrogen production. As the growing trend, brief discussions are also presented toward the high‐level assembly and manufacture of complexly structured components and devices at scale in the electrochemical and thermochemical energy systems.

Deng, Chenxin↗

Unveiling mechanism of surface-guided platinum nanowire growth

We report surface-guided growth of non-planar nanowires on functional substrates offers the new opportunity to precisely control their diameter, length, density and alignment, which will greatly benefit their direct integration into practical devices for large-scale applications. However, control of noble metal nanowires growth and arrangement remains a great challenge, and the mechanistic understanding is still limited. Herein, we choose Pt as a model material system to study the synthesis conditions required to control the in situ growth of aligned Pt nanowires on flat titanium substrate via a one-step and room-temperature green chemical synthesis process in aqueous solution. Most importantly, it is for the first time discovered that ordered nanoarrays and self-assembled nanoflowers can be directly grown on flat Ti substrate by merely adjusting the reaction times, without use of any soft/hard templates, surfactants and organic solvents. The proposed surface-guided growth mechanisms for nanoarray and nanoflower formation in this study may shed light on understanding of oriented arrangement/assembly of one-dimensional Pt nanowires into desirable morphologies for a variety of practical device applications.

Pt nanoflower↗

Thermodynamic modeling with uncertainty quantification using the modified quasichemical model in quadruplet approximation: Implementation into PyCalphad and ESPEI

The modified quasichemical model in the quadruplet approximation (MQMQA) considers the first- and the second-nearest-neighbor coordination and interactions, particularly useful in describing short-range ordering (SRO) in complex liquids such as molten salts, slag in metal processing, and electrolytic solutions. Here, the present work implements the MQMQA into the Python based open-source software PyCalphad for thermodynamic calculations. This endeavor facilitates the development of MQMQA-based thermodynamic database with uncertainty quantification (UQ) and propagation (UP) using the open-source software ESPEI. A new database structure based on Extensible Markup Language (XML) is proposed for ESPEI evaluation of MQMQA model parameters. Using the KF-NiF 2 , KCl-NaCl-MgCl 2 , and CaCl 2 -CaF 2 -LiCl-LiF salt systems as examples, we demonstrate the successful implementation of MQMQA in PyCalphad through thermodynamic calculations of Gibbs energy, equilibrium quadruplet fractions, and phase diagram, as well as database development with UQ and UP using ESPEI. Furthermore, as an application of the present implementation, both the LiF–TbF 3 and LiF-HoF 3 systems have been modeled by MQMQA for the first time, which are in good agreement with experiments. The present implementation hence offers an open-source capability for performing CALPHAD modeling for complex liquids with SRO using MQMQA plus a new XML database structure.

36 MATERIALS SCIENCE↗

Tunable broadband luminescence in lead-free hybrid copper halides

Metal halides are an important class of optoelectronic materials combining exceptional optical and electronic properties. An inherent advantage of metal halides is their solution synthesis and processability, which render them as low-cost and environmentally friendly materials for a range of applications from photovoltaics and photodetection to solid-state lighting (SSL). Here, in this study, we synthesized three previously unreported lead-free organic–inorganic hybrid copper halides: (OA) 4 CuX 5 (X = Br, I; OA + = C 8 H 17 NH 3+ , n-octylammonium cation) and (HA) 2 CuI 3 (HA + = C 6 H 13 NH 3 + , n-hexylammonium cation), all of which exhibit broadband emissions arising from self-trapped excitons (STEs). Among these compounds, (OA) 4 CuI 5 demonstrates tunable dual-band white-light emission with a high color rendering index value of 91 at room temperature. Temperature-dependent photoluminescence measurements and first-principles calculations reveal distinct behaviors between the two emission states in (OA) 4 CuI 5 . These findings highlight the potential of copper halide compounds for optoelectronic applications, particularly in the development of environmentally friendly solid-state lighting technologies.

36 MATERIALS SCIENCE↗

Polyacrylonitrile-based electrolytes: How processing and residual solvent affect ion transport and stability

Polyacrylonitrile (PAN) is one of the alternative candidate polymer hosts to form solid polymer electrolytes (SPEs) besides the widely used poly(ethylene oxide). In this study, we systematically investigate the processing of PAN based SPEs containing lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) salt, using dimethylformamide (DMF) as the solvent. The effects of PAN processing procedure including solution mixing, casting, and drying on the morphology, ion transport, solvation structure, Li and oxidative stability of PAN electrolytes are thoroughly examined. In particular, four drying conditions are investigated and the amount of residual DMF is accurately determined using infrared (IR) spectroscopy. Varying the drying conditions can lead to five orders of magnitude decrease in the ionic conductivity. As DMF content decreases, the SPE's stability again Li metal dramatically improves. The practical oxidative stability is also strongly affected by the residual DMF content, ranging from 2.5 V to 3.5 V, much lower than reported values. Finally, the role of the residual DMF solvent is elucidated. DMF content vitally influences ion solvation structure at different concentration regimes, which ultimately dictates the ion conduction mechanism and oxidative stability of PAN based SPEs. In conclusion, this thorough study lays the groundwork for future development of PAN based electrolytes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Enhancing membrane performance for CO 2 capture from flue gas with ultrahigh MW polyvinylamine

Membranes for post-combustion CO 2 capture are required to have a high CO 2 permeance due to the limited driving force. For facilitated transport membranes synthesized with polyvinylamine (PVAm), a defect-free selective layer of <200 nm is usually required to render sufficient permeance with high CO 2 /N 2 selectivity. In order to meet such a demand through the knife-coating process, the coating solution needs to have a high viscosity at a relatively low concentration to minimize its penetration into the substrate. The demand was met by synthesizing PVAm with an ultrahigh molecular weight (MW) via inverse emulsion polymerization (IEP) in this study. Compared to solution polymerization, IEP isolates the reaction in inverse micelles suspended in a continuous organic phase, which allows excellent dissipation of the heat generated by the reaction and reduces gel formation drastically. The polymerization parameters, including monomer concentration, initiator concentration, and reaction temperature, were investigated to obtain the optimal MW of PVAm for membrane performance. As compared to solution polymerization, IEP enhanced the MW of PVAm from 1.2 to 12.7 MDa, which minimized the penetration of the coating solution into the substrate and hence the extra mass transfer resistance. The effect of MW and degree of hydrolysis of PVAm on the membrane transport properties were studied. Furthermore, by employing PVAm with a MW of 12.7 MDa to strengthen the polymer matrix, the loading of piperazine glycinate in the membrane was increased up to 85 wt.%. In conclusion, the resultant membrane achieved a CO 2 permeance of 839 GPU and a CO 2 /N 2 selectivity of 161 at the typical flue gas temperature of 57°C.

20 FOSSIL-FUELED POWER PLANTS↗

Finite element modeling of electropolishing of radio frequency dipole Nb crab cavity in hydrofluoric-sulfuric acid electrolyte

The superior performance of niobium superconducting radio frequency (SRF) cavities is achieved through meticulous surface treatment, notably via chemical electropolishing, ensuring exceptionally smooth surfaces. While this technique has been extensively employed for cylindrically symmetric structures, addressing more intricate geometries poses significant challenges in achieving uniform polishing and controlled material removal, especially when moving away from retractable cathodes. This presents a multifaceted electrochemical, thermal, and fluid dynamics conundrum. A prime example is the 197 MHz radio frequency dipole (RFD) crabbing cavity proposed for the Electron Ion Collider (EIC) project, exemplifying such complex structures. Our groundbreaking work integrates the localized oxide thickness variation, considering its impact on current distribution and Joule heating, within the framework of multi-physics modeling using the COMSOL® simulation suite. This approach was applied to a comprehensive model of the RFD cavity, allowing us to investigate optimal external cooling water flow conditions necessary for achieving desirable outcomes. In conclusion, this illustrates the increasing utility of such multi-physics codes to greatly aid in designing solutions to challenging processing requirements for increasingly complex accelerator cavities.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Database-wide hazard modelling of the onset of DIII-D tearing modes with field features

The rate of onset (hazard) of tearing modes is modelled probabilistically using statistical learning algorithms. Axisymmetric energy-density equilibrium fields are taken as raw high-dimensional input features which are reduced with principal component analysis. Signal processing of non-axisymmetric magnetics fluctuation array data provides the target information from which to learn. Model selection, visualization and calibration assessment procedures are detailed. Here, the analysis is deployed at large scale across the DIII-D tokamak database. Standard model selection criteria suggest that the energy-density post-processed feature is a better choice for modelling the onset rate compared to the non-processed equilibrium reconstruction solution. Two example applications of the learned rate function are demonstrated: (i) proximity-to-onset discharge monitoring and (ii) database analysis showing an (expected) observational global trend that the general hazard increases as a plasma performance metric increases. An important connection between the hazard function and its use as a conditional probability generator is reviewed in the Appendix.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Direct Uranium Isotopic Analysis of Swipe Surfaces by Microextraction-ICP-MS

The ability to directly measure uranium isotope ratios on environmental swipes has been achieved through a solution-based microextraction process and represents a significant advancement toward the development of a rapid method to analyze international nuclear safeguard samples. Here, a microextraction probe is lowered and sealed onto the swipe surface, and analytes within the sampling site (~8 mm2) are dissolved and extracted into a flowing solvent of 2% nitric acid (HNO 3 ). The mobilized species are subsequently directed into an inductively coupled plasma-mass spectrometer (ICP-MS) for accurate and precise isotope ratio determination. This work highlights the novelty of the sampling mechanism, particularly with the direct coupling of the microextraction probe to the ICP-MS and measurement of uranium isotope ratios. The preliminary method detection limit for the microextraction-ICP-MS method, utilizing a quadrupole-based MS, was determined to be ~50 pg of 238 U. Additionally, precise and accurate isotope ratio measurements were achieved on uranium reference materials for both the major ( 235 U/ 238 U) and minor ( 234 U/ 238 U and 236 U/ 238 U) ratios. While the present work is focused on directly measuring uranium isotopic systems on swipe surfaces for nuclear safeguards and verification applications, the benefits would extend across many applications in which direct solid sampling is sought for elemental and isotopic analysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗