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Fundamental and methodological investigations for the improvement of elemental analysis by inductively coupled plasma mass soectrometry

This dissertation describes a variety of studies meant to improve the analytical performance of inductively coupled plasma mass spectrometry (ICP-MS) and laser ablation (LA) ICP-MS. The emission behavior of individual droplets and LA generated particles in an ICP is studied using a high-speed, high frame rate digital camera. Phenomena are observed during the ablation of silicate glass that would cause elemental fractionation during analysis by ICP-MS. Preliminary work for ICP torch developments specifically tailored for the improvement of LA sample introduction are presented. An abnormal scarcity of metal-argon polyatomic ions (MAr{sup +}) is observed during ICP-MS analysis. Evidence shows that MAr{sup +} ions are dissociated by collisions with background gas in a shockwave near the tip of the skimmer cone. Method development towards the improvement of LA-ICP-MS for environmental monitoring is described. A method is developed to trap small particles in a collodion matrix and analyze each particle individually by LA-ICP-MS.

36 MATERIALS SCIENCE↗

Modeling Adjustable Speed Pumped Storage Hydro Units Employing Doubly-Fed Induction Machines

This report is a part of a series of documents to be issued in the course of a U.S. Department of Energy (DOE) project titled “Modeling and Analysis of Value of Advanced Pumped Storage Hydropower in the U.S.” The purpose of this report is to propose a model structure for an adjustable speed pumped storage hydro (PSH) unit employing a doubly-fed induction machine (DFIM). The use of a DFIM with its rotor windings controlled by a power converter is the present state-of-the-art design for adjustable speed hydro pumped storage units. Although the theoretical basis for the analysis of DFIMs was developed at least 70 years ago (a paper by Charles Concordia et al. in 1942 describes the mathematical modeling and dynamic response of DFIM and refers to even earlier publications), it seems appropriate to provide the fundamental equations governing their dynamic behavior so that the following discussions on modeling these devices for stability studies are more meaningful.

Koritarov, Vladimir↗

Multi-Collector Inductively Coupled Plasma Mass Spectrometer – Operational Performance Report

The INL made an assessment of the commercially available inductively coupled plasma mass spectrometers (ICPMS) for actinide analysis; emphasizing low detection limits for plutonium. INL scientists subsequently determined if plutonium was present on a swipe, at a 10 million atom decision level. This report describes the evaluation of ICPMS instruments and the operational testing of a new process for the dissolution, separation and analysis via ICPMS of swipes for plutonium and uranium. The swipe dissolution, plutonium and uranium isolation, separation and purification are wet chemistry methods following established procedures. The ICPMS is a commercially available multi-collector magnetic sector mass spectrometer that utilizes five ion counting detectors operating simultaneously. The instrument includes a sample introduction system allowing for sample volumes of < 1 mL to be reproducibly injected into the instrument with minimal waste of the sample solution, while maximizing the useable signal. The performance of the instrument was measured using SRM 996 ( 244 Pu spike) at concentrations of 12 parts per quadrillion (ppq, fg/mL) and with SRM 4350B Columbia River Sediment samples spiked onto swipes at the 10 million atom level. The measured limit of detection (LOD, defined as 3s) for 239 Pu is 310,000 atoms based upon the instrument blank data. The limit of quantification (LOQ defined as 10 s) for 239 Pu is 105,000 atoms. The measured limit of detection for 239 Pu from the SRM 4350B spiked onto a swipe was 2.7 million atoms with the limit of quantification being 9.0 million atoms.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Retuning the DARHT Axis-II Linear Induction Accelerator

The Dual-Axis Radiographic Hydrodynamic Test (DARHT) facility uses bremsstrahlung radiation source spots produced by the focused electron beams from two linear induction accelerators (LIAs) to radiograph large hydrodynamic experiments driven by high explosives. The Axis-II 1.7-kA, 1600-ns beam pulse is transported through the LIA by the magnetic field from 91 solenoids as it is accelerated to ~16.5 MeV. The magnetic field produced by the solenoids and 80 steering dipole pairs for a given set of magnet currents is known as the “tune” of the accelerator [1]. From June, 2013 through September, 2014 a single tune was used. This tune was based on measurements of LIA element positions made over several years [2], and models of solenoidal fields derived from actual field measurements [3] [4]. Based on the focus scan technique, changing the tune of the accelerator and downstream transport had no effect on the beam emittance, to within the uncertainties of the measurement. Beam sizes appear to have been overestimated in all prior measurements because of the low magnification of the imaging system. This has resulted in overestimates of emittance by ~50%. The high magnification imaging should be repeated with the old tune for direct comparison with the new tune. High magnification imaging with the new accelerator tune should be repeated after retuning the downstream to produce a much more symmetric beam to reduce the uncertainty of this measurement. Thus, these results should be considered preliminary until we can effect a new tune to produce symmetric spots at our imaging station, for high magnification images.

43 PARTICLE ACCELERATORS↗

Demonstration of femtosecond laser ablation inductively coupled plasma mass spectrometry for uranium isotopic measurements in U-10Mo nuclear fuel foils

The use of femtosecond laser ablation inductively coupled plasma mass spectrometry was used to demonstrate the feasibility of measuring the isotopic ratio of uranium directly in U-10Mo fuel foils. The measurements were done on both the flat surface and cross sections of bare and Zr clad U-10Mo fuel foil samples. The results for the depleted uranium content measurements were less than 10% of the accepted U235/238 ratio of 0.0020. Sampling was demonstrated for line scans and elemental mapping over large areas. In addition to the U isotopic ratio measurement, the Zr thickness could be measured as well as trace elemental composition if required. A number of interesting features were observed during the feasibility measurements which could provide the basis for further investigation using this methodology. The results demonstrate the feasibility of using fs-LA-ICP-MS for measuring the U isotopic ratio in U-10Mo fuel foils.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Comparison of femtosecond and nanosecond laser ablation inductively coupled plasma mass spectrometry for uranium isotopic measurements

Feasibility tests were conducted using femtosecond and nanosecond laser ablation inductively coupled plasma mass spectrometry for rapid uranium isotopic measurements. The samples used in this study consisted of a range of pg quantities of known 235/238 U solutions as dried spot residues of 300 pL drops on silicon substrates. The samples spanned the following enrichments of 235 U: 0.5, 1.5, 2, 3, and 15.1%. In this direct comparison using these particular samples both pulse durations demonstrated near equivalent data can be produced on either system with respect to accuracy and precision. There is no question that either LA-ICP-MS method offers the potential for rapid, accurate and precise isotopic measurements of U10Mo materials whether DU, LEU or HEU. The LA-ICP-MS equipment used for this work is commercially available. The program is in the process of validating this work for large samples using center samples strips from Y-12 MP-1 LEU-Mo Casting #1.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A model of annular linear induction pumps

The present work explains how the magnetic field and the induced current are obtained when the distributed coils are powered by a 3 phase power supply. From the magnetic field and the induced current, the thrust and the induction losses in the pump can be calculated to estimate the pump performance.

42 ENGINEERING↗

Diagnostic studies of ion beam formation in inductively coupled plasma

This dissertation describes a variety of studies focused on the plasma and the ion beam in inductively coupled plasma mass spectrometry (ICP-MS). The ability to use ICP-MS for measurements of trace elements in samples requires the analytes to be efficiently ionized. Updated ionization efficiency tables are discussed for ionization temperatures of 6500 K and 7000 K with an electron density of 1 x 10 15 cm -3 . These values are reflective of the current operating parameters of ICP-MS instruments. Calculations are also discussed for doubly charged (M 2+ ) ion formation, neutral metal oxide (MO) ionization, and metal oxide (MO + ) ion dissociation for similar plasma temperature values. Ionization efficiency results for neutral MO molecules in the ICP have not been reported previously.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Trace metal analysis by laser ablation-inductively coupled plasmamass spectrometry and x-ray K-edge densitometry of forensic samples

This dissertation describes a variety of studies on the determination of trace elements in samples with forensic importance. Laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) was used to determine the trace element composition of numerous lipstick samples. Lipstick samples were determined to be homogeneous. Most lipstick samples of similar colors were readily distinguishable at a 95% confidence interval based on trace element composition. Numerous strands of a multi-strand speaker cable were analyzed by LA-ICP-MS. The strands in this study are spatially heterogeneous in trace element composition. In actual forensic applications, the possibility of spatial heterogeneity must be considered, especially in cases where only small samples (e.g., copper wire fragments after an explosion) are available. The effects of many unpredictable variables, such as weather, temperature, and human activity, on the retention of gunshot residue (GSR) around projectile wounds were assessed with LAICP- MS. Skin samples around gunshot and stab wounds and larvae feeding in and around the wounds on decomposing pig carcasses were analyzed for elements consistent with GSR (Sb, Pb, Ba, and Cu). These elements were detected at higher levels in skin and larvae samples around the gunshot wounds compared to the stab wounds for an extended period of time throughout decomposition in both a winter and summer study. After decomposition, radiographic images of the pig bones containing possible damage from bullets revealed metallic particles embedded within a number of bones. Metallic particles within the bones were analyzed with x-ray, K-edge densitometry and determined to contain lead, indicating that bullet residue can be retained throughout decomposition and detected within bones containing projectile trauma.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Additive Manufacturing Consolidation of Low-Cost Water Atomized Steel Powder Using Micro-Induction Sintering

ORNL worked with Grid Logic Inc to demonstrate micro induction sintering (MIS) and binder decomposition of steel powders. It was shown that MIS effectively emits spatially confined electromagnetic energy that is directly coupled to metallic powders resulting in resistive heating of individual particles. The non-uniformity of particle morphology and distribution of the water atomized steel powders resulted in inefficient transfer of energy. It was shown that adhering the particles together using polymer binders resulted in more efficient coupling. Using the MIS processes, debinding and sintering could be done in a single step. When combined with another system, such as binder-jet, this could reduce the amount of required post-processing. An invention disclosure was filed on hybrid systems that use MIS to reduce the amount of required post-processing.

36 MATERIALS SCIENCE↗

Beam Breakup in a Solid-State Powered Linear Induction Accelerator

Scorpius is a new multi-pulse linear induction accelerator (LIA) for flash radiography of large-scale, explosively-driven hydrodynamic experiments. It has been proposed to use solid-state pulsed-power modules to provide the accelerating voltages for Scorpius. It is expected that this approach can provide four programmable 50-kV accelerating pulses to a single gap.

43 PARTICLE ACCELERATORS↗

Optimum tunes for the DARHT and Scorpius linear induction accelerators

A systematic approach to design of optimum magnetic focusing tunes for linear induction accelerators (LIA) is described. The magnetic fields used for focusing and beam transport must be strong enough to suppress beam breakup, yet not so strong that they induce envelope instability. Balancing these objectives, while also minimizing magnet power requirements, results in the optimum tune.

43 PARTICLE ACCELERATORS↗

Induction Heating for Tritium Storage Beds (FY19 PDRD Project Summary Report)

Metal hydride beds used for storing hydrogen isotopes at the Savannah River Site are conductively heated and cooled to desorb and absorb gases during storage cycling. While several storage bed configurations have been utilized over the years, many achieve heating by utilizing electric cartridge heaters positioned laterally along the longest axis of the storage bed (FACE Gen 2 Beds). Others achieve heating and cooling through hot and cold nitrogen flow (Gen 1 Beds). While these beds/heating configurations are well-designed for storage cycling operations, it is unclear if they can be regenerated to operating conditions once too much helium has accumulated in them. Full regeneration of hydride beds occurs around 625 - 650 °C. It is unclear if the currently employed electric cartridge heaters in Gen 2 beds can reach these temperatures. Furthermore, since swelling can occur during routine heating operations, it is unclear if existing cartridge heaters in Gen 2 beds can be swapped for higher-power cartridges that can reach 625 - 650 °C . Similarly, nitrogen air flow (to the best of our knowledge) cannot cause Gen 1 beds to reach these temperatures. Thus, existing Gen 1 and Gen 2 beds need to be heated through an alternative method to removal helium, so the beds can either return to normal operation or be disposed of. The goal of this PDRD was to investigate if induction heating can be used for various heating processes involving hydride storage beds (e.g. regeneration, gas cycling, helium heel removal). In the original call for proposals, this PDRD fell under "Gas Processing" area of interest # 3: "Develop methods to deploy alternate ways to heat existing process equipment to minimize impact to glove box environment."

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Linear Induction Accelerator Cell Voltage Calibration Using Compact Electron Permanent Magnet Spectrometer

The Dual-Axis Radiographic Hydrodynamic Test (DARHT) facility provides flash radiography capabilities using electron Linear Induction Accelerators (LIA’s). The strict requirements for flash radiography require a detailed understanding of the LIA’s performance, including precision measurements of the electron beam energy. Axis-1 of DARHT produces a 20 MeV, 2 kA, 80-ns-FWHM electron beam. Electronic measurement with cell-voltage monitors which consists of a 75 ohm load resistor and a current viewing resistor (CVR) that are coupled together and injector capacitive monitors (EVACSUM) are summed to give the total beam energy at the output of the accelerator. Calibration of these monitors was last done in 1999 and is needed. Using the Compact electron Permanent Magnet Spectrometer (CePMSpec), we have developed a technique for measuring and adjusting the calibration of the accelerator cell load resistor/CVR by using the total energy of the beam. Each pair of cells is driven by pulsed power Blumleins, and each Blumlein is charged by a Blumlein Charge Unit (BCU). There are 64 cells and 32 Blumleins and BCUs. This technique is applied to all 32 BCUs.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Concurrent evaluation of autophagy induction and Burkholderia infection at the single cell level

Autophagy is a natural, regulated cellular process that "cleans up" cellular debris by degrading and recycling dysfunctional proteins. There is a high potential impact of exploiting the benefits of autophagy to complement existing treatments, but little has been done to date on bacterial pathogens of defense concern such as Burkholderia pseudomallei, a highly virulent Select Agent pathogen that is intrinsically resistant to most classes of antibiotics. Assessment of autophagy in the context of infection typically requires use of multiple technologies in combination (e.g., Western analysis paired with microscopy or flow cytometry) as applied to heterogeneous populations of cells. To address this, we have developed a dual target reporter cell line (RAW264.7 LC3-BFP:mPlum, GFP-RelA) that enables concurrent visualization of infection and autophagy induction. We assessed the effect of clinically approved small molecule inducers of autophagy on infection by Burkholderia thailendensis, a closely related but less virulent surrogate for B. pseudomallei. The reporter cells were first infected with a B. thailendensis strain that constitutively expresses GFP, then treated with one of four known autophagy inducers (rapamycin, niclosamide, bromhexine HC1, or flubendazole) for 4 hours. Confocal fluorescence imaging was used to quantify autophagy stimulation at the single cell level. Autophagy maturation was observed as a decrease in BFP LC3 puncta with a concurrent increase in mPlum LC3 puncta. B. thailendensis infection was assessed by monitoring translocation of GFP-RelA (an NFkB subunit) into the nucleus and through quantitating the intracellular bacterial presence in single cells. Preliminary results indicate that bromhexine HC1 and niclosamide may hinder B. thailendensis' ability to replicate intracellularly and reduce overall bacterial survival.

59 BASIC BIOLOGICAL SCIENCES↗

Initial conditions for simulations of beam physics in linear induction accelerators

Flash radiography of hydrodynamic experiments driven by high explosives is a well-known diagnostic technique in use at many laboratories. At Los Alamos, the DualAxis Radiographic Hydrodynamic Test (DARHT) facility two linear induction electron accelerators (LIAs) make the bremsstrahlung radiographic source spots for point projection radiographs from orthogonal views. A new LIA, called Scorpius, is presently under development to advance this technology. To better understand electron-beam physics in these LIAs, numerical simulations are frequently performed with the objective of improving the radiography. At Los Alamos we frequently use the TRAK ray-trace and LSP particle-in-cell (PIC) codes to simulate the injector, and the XTR and LAMDA envelope/centroid codes along with LSP to simulate transport of the accelerated beam through the LIAs. The LIA simulations need the injected beam parameters as initial conditions for calculating beam transport and stability. The determination of these initial conditions is the topic of this note.

43 PARTICLE ACCELERATORS↗

Magnetic Induction Sensors for Detecting Anomalous Shielding of Radiological and Nuclear Materials: A Feasibility Study

This study examined a concept for improving the nation's ability to detect unauthorized transport of radiological and nuclear material that involves detecting not the radiological or nuclear material itself, but rather the anomalous presence of materials, such as lead and tungsten, typically used to shield such illicit materials from detection. Specifically, the project studied a potentially inexpensive, non-intrusive, and fast method of detecting anomalous shielding: use of magnetic induction sensors to measure currents induced in conductors by a driver coil. The first phase of this work, documented in this report, identified the signatures of materials of interest, assessed the usefulness of measured signatures for discrimination between materials, and then benchmarked models and calculations. The next task involved assessing the strength of these signatures when the materials of interest were enclosed within other materials, such as aluminum and steel, of various thicknesses. A final task mimicked a real-world scenario by testing the ability to detect material signatures of interest at a scale of a vehicle or cargo vessel against a cluttered backdrop, with and without the shielding of another material, such as aluminum or steel. This final task raised doubts regarding whether this detection scheme will be useful under real-world conditions.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗