Radiochemistry Commons^™

Women As A Force Multiplier For Bringing Nuclear Forensic Capabilities To The International Stage, Heather M. Dion, Caterina Fox, Kim Knight, Anne Phillip

International Journal of Nuclear Security

In 2009, the US Department of Energy National Nuclear Security Administration’s (NNSA’s) Defense Nuclear Nonproliferation Program initiated a new nuclear forensics outreach effort under its Confidence Building Measures Program. Little did they know that the timing could not have been better. This article focuses on the early years (2009–2015) of the NNSA’s international nuclear forensics outreach, specifically the efforts and experiences of the women who helped establish this program, building it from a fledgling, bilateral effort into an enduring technical capacity provider engaging with dozens of countries and multilateral organizations. At the onset of the program, nuclear forensics was an …

The Effect Of Hydrogen Peroxide On The Corrosion Dynamics Of Carbon Steel, Kwang Soak Gabriel O'Donnell

Electronic Thesis and Dissertation Repository

The Used Fuel Container (UFC) is a key barrier in Canada’s nuclear fuel disposal plan. Understanding the radiation-induced corrosion of the carbon steel (CS) vessel is critical for predicting the long-term integrity of the UFC. Developing a mechanistic understanding of CS corrosion and the effect of solution parameters is essential.

This work investigates the effects of H₂O₂, the key radiolytic oxidant, on CS corrosion dynamics in small, stagnant solutions. Elementary processes are identified, corrosion rates are calculated, and the effects of H₂O₂ concentration are investigated. Corrosion was studied by quantifying the concentrations of …

Analytical Techniques For The Analysis Of Uranium Bearing Materials, Nathaniel D. Fletcher

Doctoral Dissertations

The interest in the use of nuclear power has increased drastically in recent years. This is due to significantly increased efficiency at producing energy when compared to fossil fuels. With the increased use of nuclear power comes an increased need to for monitor for uranium bearing materials outside of regulatory control. This dissertation covers four projects aimed at improving the analysis of these materials. The first projects aims to develop a method that allows for the analysis of elements that exist in nature as anions by triple quadrupole ICP – MS. This would allow for the ability to measure more …

Near-Ir Laser Ablation Of Simulated Radiologically Contaminated Oxides On Carbon Steel Feeder Pipes, Thao Viet Do

Electronic Thesis and Dissertation Repository

As nuclear power plants age and retire from service, many countries face significant challenges concerning the safe long-term storage and disposal of large volumes of low and intermediate level radioactive wastes (L&ILW). The volumes of metallic waste are of particular concern, as when metal corrodes it produces hydrogen that could lead to pressure build-up in interim storage and disposal. In Canada, a significant fraction of the metallic wastes for Canada Deuterium Uranium (CANDU) nuclear reactors are out-of-core reactor components, such as carbon steel (CS) feeder pipes. The radioactive contamination is expected to be largely confined to the surface oxide layers …

Ligands For Complexation, Extraction, And Sensing Of Mercury(Ii) For Application To High-Level Waste (Hlw) At The Savannah River Site (Srs), Adenike O. Fasiku

FIU Electronic Theses and Dissertations

Mercury (Hg) separation and sensing is of high significance due to Hg^(II) environmental mobility and toxicity. Furthermore, the use of Hg in nuclear applications has resulted in its accumulation in several DOE sites, such as in Oak Ridge and Savannah River reservations. Organic mercury species have been found in low activity waste (LAW) streams resulting from high-level waste (HLW) processing at the Savannah River Site (SRS), therefore posing a threat to humans and the environment. Mercury, being a soft Lewis acid, has a strong affinity for softer Lewis bases, such as S- or N-donor ligands. Therefore, we focus on …

Uranium Fate And Mineral Transformations Upon Remediation With Ammonia (Nh3) Gas, Silvina A. Di Pietro

FIU Electronic Theses and Dissertations

The fission of uranium (U) for plutonium production was a major activity at the U.S. Department of Energy’s (DOE) Hanford Site in Washington State during World War II and Cold War. This endeavor resulted in the generation of over two million liters of high-level radioactive waste, most of which still remains in 177 underground storage tanks. Due to the improper storage and aging of these tanks in addition to other waste releases across the Site, approximately 200,000 kg of U have been released into the vadose zone. The objective of this study was to determine whether the application of the …

Galvanic Corrosion Of Carbon Steel-Stainless Steel Welds, Mi Li

Electronic Thesis and Dissertation Repository

A water leak in one of the Canada Deuterium Uranium (CANDU) nuclear reactors could lead to galvanic corrosion between the materials of its supporting structures: carbon steel (CS) and stainless steel (SS). This project investigates the effects of physical and chemical solution parameters on the corrosion of galvanically coupled dissimilar CS-SS welds, with the aim of developing a corrosion dynamics model that can be used to assess the long-term integrity of the CANDU reactor structural materials with confidence. The studied parameters were solution pH, temperature, the presence or absence of γ-radiation and the cathode:anode surface area ratio. Multiple electrochemical techniques …

Separation Of Neighboring Trivalent Lanthanides For Neutron Capture Cross Section Measurements, Balazs Jozsef Bene

UNLV Theses, Dissertations, Professional Papers, and Capstones

The determination of the low-energy neutron capture cross-section of 171Tm with greater accuracy is important for both astrophysics and Stockpile Stewardship. Thulium-171 is a branching point in the s-process of stellar nucleosynthesis. Branching point nuclei, with half-lives in the order of 1 – 100 years are places where neutron capture and beta decay competes. This isotope is also the second order (n, γ) reaction product of 169Tm, which was used as a radiochemical detector in nuclear weapon experiments. It was placed at strategic locations in nuclear devices. Following the test, samples were analyzed in the collected samples for products of …

Evolution Of Cu2o Morphology During Copper Corrosion In The Presence Of Gamma-Radiation, Arielle M. Jean

Electronic Thesis and Dissertation Repository

In this work, experiments were carried out in order to develop a mechanistic understanding of the corrosion of copper metal in limited water volumes under gamma-radiation. When exposed to gamma-radiation, water decomposes into chemically reactive oxidizing and reducing species. Under a continuous radiation flux, the concentrations of the radiolytically produced oxidants eventually reach a pseudo-steady state that can influence the corrosion kinetics of metallic surfaces.

The evolution of the surface morphology during water droplet corrosion of copper in the presence of gamma-radiation was investigated as a function of irradiation time and pH. The oxide growth kinetics were studied by measuring …

Development Of Neurotensin-Based Radiopharmaceuticals For Neurotensin-Receptor-1-Positive Tumors Targeting, Yinnong Jia

Theses & Dissertations

The neurotensin receptor 1 (NTR1) is overexpressed in many cancers, due to its role as a growth pathway. These NTR1-positive cancers include pancreatic, colon, prostate and breast cancers. In the radiopharmaceutical field, the overexpression of NTR1 in cancer has prompted the development of NTR1-targeted diagnostics and therapeutics. The neurotensin (NT) peptide exhibits low nanomolar affinity for NTR1 and has been the paradigm for NTR1-targeted agents. Since the 1980’s, radiolabeled NT analogs have been developed and evaluated for targeting NTR1-positive cancers. Since native NT is rapidly degraded in vivo by a variety of peptidases, a tremendous amount of effort has been …

Improved Sample Utilization In Thermal Ionization Mass Spectrometry Isotope Ratio Measurements: Refined Development Of Porous Ion Emitters For Nuclear Forensic Applications, Matthew Louis Baruzzini

Doctoral Dissertations

The precise and accurate determination of isotopic composition in nuclear forensic samples is vital for assessing origin, intended use and process history. Thermal ionization mass spectrometry (TIMS) is widely accepted as the gold standard for high performance isotopic measurements and has long served as the workhorse in the isotopic ratio determination of nuclear materials. Nuclear forensic and safeguard specialists have relied heavily on such methods for both routine and atypical efforts. Despite widespread use, TIMS methods for the assay of actinide systems continue to be hindered by poor ionization efficiency, often less than tenths of a percent; the majority of …

Development Of An F-Element Separation Chemistry Using Solid Electrolytes, Kristian Guy Myhre

Doctoral Dissertations

The f‒elements (lanthanides and actinides) have numerous applications and are critically important to many industries, including the energy, security, and medical industries. One of the barriers to increased use and availability of the f‒elements is the difficulty in separating them from each other due to their similar chemistries. This is especially true of the trivalent f‒elements (lanthanides and minor actinides). The development of separation techniques that maximize the differences in the physicochemical properties of the f‒elements is therefore an important area of research. For these reasons, an effort was undertaken to explore the use of solid …

Interference Effects Of Urban Rubble On The Radioanalytical Analysis Of Strontium, Derek Roger Mclain

UNLV Theses, Dissertations, Professional Papers, and Capstones

Most current radioanalytical protocols have been developed for the analysis of air, water, soil and bioassay samples. While these protocols build the foundation of operational environmental monitoring, they are not necessarily suitable for the analysis of samples that will be encountered in the aftermath of a nuclear incident. In such a situation, it will be important to characterize the isotopes of interest present in the affected area to obtain signatures for nuclear forensics and ensure the appropriate response. Specifically, this research is aimed at the determination of strontium-90 and its separation from zirconium-90 in a post-detonation situation.

Strontium-90’s relatively long …

Cd Transport In Eutectic Licl-Kcl And Contamination Of Zr Metal And Thermal Dehydration Of Bulk Licl-Kcl, Nicholas Azoy Earle

Masters Theses

Researchers at Idaho National Labs have noted unexpectedly high Cd content in empty cladding hulls after processing in the Mark-IV ER. It has been theorized that Cd metal is transporting from the LCC pool through the eutectic LiCl-KCl salt bath to the anode baskets containing the empty hull where it is retained as a Zr-Cd intermetallic. This study sought to replicate the Cd contamination in a dry Ar glovebox using small-scale analogue of the Mark-IV ER salt-Cd metal system.

Anhydrous eutectic LiCl-KCl was an essential regent in this research and experiments were conducted to investigate the feasibility of dehydrating nominally …

Investigation Of 89zr-Siderophores As Molecular Imaging Agents For Positron Emission Tomography Imaging Of Bacterial Infections, Nora C. M. Goscinski

Arts & Sciences Electronic Theses and Dissertations

Siderophores are small molecules synthesized by bacteria to harvest Fe³⁺ from their environment. In infection scenarios, their production can increase infection virulence by increasing the ability of bacteria to obtain Fe³⁺ and therefore grow more rapidly. The selective uptake of siderophores in vivo in multi-bacteria environments indicates that this class of molecules has a potential use as selective imaging agents. In this work, DFO-NCS and a library of trihydroxamate siderophores were evaluated as vehicles to deliver ⁸⁹Zr selectively to bacteria for Positron Emission Tomography (PET) imaging of bacterial infections.

Productive work with radiometals involves thorough knowledge of …

Advances In High-Throughput Analysis: Automated Radiochemical Separations And Nanopillar Based Separations And Field Enhanced Spectroscopy, Jennifer Jeanne Charlton

Doctoral Dissertations

Often the need to analyze a large number of samples coincide with critical time consternates. At such times, the implementation of high-throughput technologies is paramount. In this work we explore some viable pathways for high-throughput analysis and develop advancements in novel forms of detection of materials that are vital in the environmental, biological as well as national security arenas. Through the use of new protocols with high sensitivity and specificity as well as simplified chemical processing and sample preparation we aim to allow for improved throughput, fieldable detection, and rapid data acquisition of extensive sample sets. The methods developed in …

Impurity Diffusion As A Possible Metal Chronometer For Pre-Detonation Nuclear Forensics, Edward T. Peskie, Howard L. Hall

International Journal of Nuclear Security

The ability to determine the age of seized nuclear material—that is, the time that has passed since it was formed— would provide crucial data to be used in its investigation. This paper reviews the methods and mathematical reasoning behind the use of diffusion theory, as previously applied to analysis of metals in ancient artifacts and other objects, to modern investigations in nuclear science. We here examine the time-dependent processes of diffusion, including grain boundary diffusion and discontinuous precipitation, and we assess the utility of examining the profiles of impurity and alloying element concentrations for use as a tool in pre-detonation …

An Investigation Of Inorganic Compound Scattering., Karl Jay Bernstein

Doctoral Dissertations

Raman and its associated forms of spectroscopy are powerful tools that have been under-utilized. Presented within are three inorganic compounds studied with some form of Raman spectroscopy: normal Raman, hyper-Raman (HR), surface-enhanced Raman spectroscopy (SERS), surface-enhanced hyper-Raman spectroscopy (SEHRS), or resonance Raman spectroscopy (RR).

The first study involves the investigation of phosphine binding with silver metal. Phosphines find wide use in synthetic circles yet have had little study into their method of binding, unlike similar compounds comprised of sulfur. In order to understand the binding of phosphines, several tertiary phosphines, secondary phosphines and secondary phosphine oxides are examined with SERS. …

Green Chemistry As A Tool For Understanding The Toxic Substances Control Act: A Lecture Module For Undergraduate Students, Molly R. Blessing

Honors Scholar Theses

The Toxic Substances Control Act (TSCA) is the central form of chemical regulation existent in the United States today, yet scientists are often unaware or uncertain of its provisions. Violations of TSCA by unknowing chemists set industry and government unnecessarily at odds. A lecture on TSCA was developed for undergraduate students that uses the concept of green chemistry to promote interest and incentivize learning. Green chemistry methods are cleaner and less wasteful than traditional chemical ones, and many companies using them are at the forefront of technological innovation. The lecture explains both green chemistry and TSCA, includes company case studies, …

Simultaneous Determination Of Multiple Actinide Elements In A Variety Of Soils Utilizing A Standardized Sequential Extraction Protocol, Sherry Alina Faye

UNLV Theses, Dissertations, Professional Papers, and Capstones

To obtain a better understanding of the mobility of actinide element contaminants in the environment, the association of the contaminants with specific host phases of soils and sediments must be investigated. This investigation is most commonly conducted using sequential extraction techniques that employ the selective dissolution of soil phases with increasingly aggressive chemical treatment. Though several sequential extraction studies exist in literature, conclusions cannot be made by direct comparison of data due to the lack of uniformity in the protocols used. This work aims to continue development of a standard sequential extraction protocol and expanding its capabilities to include the …

Effect Of Gamma Radiation On The Interfacial Reactions And Transfer Processes Of Phosphonium-Based Ionic Liquids With Carbon Steel, Ryan P. Morco

Electronic Thesis and Dissertation Repository

This thesis presents work on the effects of ionizing radiation on phosphonium-based ionic liquids (ILs). Ionic liquids are known for their tunable properties which make them attractive options for applications for the separation and sequestration of metal ions from spent nuclear fuels, and candidate lubricants for systems under severe conditions. The high radiation environment found in spent fuel processing may decompose the solvents (ILs) used in the process and affect their separation efficiency. The radiolytic decomposition products can also alter the physical and chemical properties of an IL in ways which can affect the potential corrosion of metal alloys in …

The Electrochemistry Of Hydrogen Peroxide On Uranium Dioxide And The Modelling Of Used Nuclear Fuel Corrosion Under Permanent Disposal Conditions, Linda Wu

Electronic Thesis and Dissertation Repository

This thesis reports a series of investigations examining the corrosion process of used nuclear fuel under permanent disposal conditions. The motivation of the project is that the safety assessment of deep geological disposal of spent nuclear fuel requires a fundamental understanding of the processes controlling fuel corrosion which could lead to the release of radionuclides to the geosphere from a failed container.

One primary objective of this project was to develop a computational model in order to simulate fuel corrosion under the disposal conditions. A series of simulations based on COMSOL were designed and developed to determine the influence of …

Comparative Metabolism Of Phenanthro[3,4-B]Thiophene And Benzo[C]Phenanthrene, Jaquan M. Williams

Jaquan M Williams

ABSTRACT OF THESIS Comparative Metabolism of Phenanthro[3,4-b]Thiophene And Benzo[c]Phenanthrene Polycyclic aromatic hydrocarbons (PAHs) and their sulfur-heterocyclic analogs (thia-PAHs) are commonly occurring persistent environmental contaminants formed by incomplete combustion of organic matter. A number of thia-PAHs have shown significant mutagenic and carcinogenic activities. As noted with PAHs, these chemical contaminants also require metabolic activation in order to exhibit their mutagenic and carcinogenic effects. In the present study, a comparison of the metabolism of highly mutagenic phenanthro[3,4-b]thiophene (P[3,4-b]T) and its weakly mutagenic carbon analogue, benzo[c]phenanthrene (B[c]P), was investigated. Metabolism studies were conducted using liver microsomes from induced rats, un-induced rats, as well …

Separation Of Tc From U And Development Of Metallic Tc Waste Forms, Edward Mausolf

UNLV Theses, Dissertations, Professional Papers, and Capstones

The isotope Technetium-99 (⁹⁹Tc) is a major fission product of the nuclear industry. In the last decade, approximately 20 tons of 99Tc have been produced by the US nuclear industry. Due to its long half-life (t_1/2 = 214,000 yr), beta radiotoxicity, and high mobility as pertechnetate [TcO₄]^-, Tc represents long-term concern to the biosphere. Various options have been considered to manage ⁹⁹Tc. One of them is its separation from spent fuel, conversion to the metal and incorporation into a metallic waste form for long-term disposal. After dissolution of spent fuel in nitric …

Molecular Forensic Science Analysis Of Nuclear Materials, Dallas Reilly

UNLV Theses, Dissertations, Professional Papers, and Capstones

Concerns over the proliferation and instances of nuclear material in the environment have increased interest in the expansion of nuclear forensics analysis and attribution programs. A new related field, molecular forensic science (MFS) has helped meet this expansion by applying common scientific analyses to nuclear forensics scenarios. In this work, MFS was applied to three scenarios related to nuclear forensics analysis. In the first, uranium dioxide was synthesized and aged at four sets of static environmental conditions and studied for changes in chemical speciation. The second highlighted the importance of bulk versus particle characterizations by analyzing a heterogeneous industrially prepared …

Intragroup Separation Of Trivalent Lanthanides And Actinides For Neutron Capture Experiments In Stockpile Stewardship Sciences, Narek Gharibyan

UNLV Theses, Dissertations, Professional Papers, and Capstones

Knowledge of low-energy cross sections for stable and unstable nuclei in neutron-, γ- and ion induced reactions is important in both the simulation and radiochemistry diagnosis of nuclear device performance. This dissertation explores extraction chromatography and ion chromatography methods for the intragroup separation of trivalent actinides and lanthanides in support of cross section measurements for isotopes of interest. For trivalent actinides, americium (Am(III)) and curium (Cm(III)), separation is necessary to assist in experiments related to the measurement of neutron capture cross section for ²⁴¹ Am and the production of ^{242 m} Am/^242g Am isomeric ratio. Extraction chromatography resins …

Equilibrium Speciation Of Select Lanthanides In The Presence Of Acidic Ligands In Homo- And Heterogeneous Solutions, Troy Robinson

UNLV Theses, Dissertations, Professional Papers, and Capstones

This dissertation explores lanthanide speciation in liquid solution systems related to separation schemes involving the acidic ligands: bis(2-ethylhexyl) phosphoric acid (HDEHP), lactate, and 8-hydroxyquinoline. Equilibrium speciation of neodymium (Nd³⁺ ), sodium (Na⁺ ), HDEHP, water, and lactate in the TALSPEAK liquid-liquid extraction system was explored under varied Nd³⁺ loading of HDEHP in the organic phase and through extraction from aqueous HCl and lactate media. System speciation was probed through vapor pressure osmometry, visible and Fourier Transform Infrared (FTIR) spectroscopy, ²² Na and ¹³ C labeled lactate radiotracer distribution measurements, Karl Fischer titrations, and equilibrium pH measurements. Distribution …

Synthesis, Extraction, Dissolution, And Voltammetry Of F-Species In A Room Temperature Ionic Liquid Solvent, Wendy Jacqueline Pemberton

UNLV Theses, Dissertations, Professional Papers, and Capstones

Room temperature ionic liquids (RTILs) are salts that are liquids from as low as -96 °C to up to 100 °C. RTILs are of high interest in many fields of study because of their negligible vapor pressure, high electrochemical stability, high conductivity, and wide electrochemical windows. These diverse solvents have recently been used in organic synthesis, as extraction solvents, and as electrochemical solvents. It is as a direct result of the multifunctional capabilities of these RTIL solvents that they are examined in this work. The ability to probe the chemistry of lanthanides and actinides is based on the unique properties …

Extraction Chromatographic Studies Of Rutherfordium And Dubnium Homologs, Megan E. Bennett

UNLV Theses, Dissertations, Professional Papers, and Capstones

Studying the chemistry of transactinide elements does not only allow for these elements to be properly placed in the Periodic Table, but it also permits for the extrapolation of the electronic structure based upon the position of the element in the Periodic Table. In addition it enable for the assessment of the role that relativistic effects play in the chemical behavior of the heaviest elements. An improved understanding of the role of relativistic effects in chemistry of the heaviest elements allows for a better understanding of the fundamentals principles that govern the Periodic Table. In order to investigate the chemistry …

Preparation And Characterization Of Extraction Chromatography Resins Using N-Donor Extractants For Trivalent Actinide And Lanthanide Separations, Christopher L. Klug

UNLV Theses, Dissertations, Professional Papers, and Capstones

Actinide and lanthanide elements exist in the geosphere and biosphere due to both natural abundances and anthropogenic activities. The investigation of the presence and transport of actinides through the environment is of great scientific interest. In order to prepare environmental samples for precise measurements, the individual actinides must be separated from the chemically similar lanthanides, and from neighboring actinides. Existing extraction chromatography resins are either poorly suited for this separation, have bleeding problems, are not reusable, or fail the CHON principle. In an effort to resolve these issues, malonamides and N-donor extractants from the BTP and BTBP classes of solvent …