Radiochemistry Commons^™

The Behavior And Complexation Of Technetium Under Conditions Relevant For Nuclear Fuel Reprocessing, Rachel E. Greenberg

Dissertations, Theses, and Capstone Projects

Spent nuclear fuel is reprocessed by utilizing several large-scale solvent extraction processes. One of the most prevalent of these processes is the plutonium uranium reduction extraction (PUREX) process. This process involves an organic phase composed of tributyl phosphate (TBP) in kerosene and an aqueous phase comprised of concentrated nitric acid. Both uranium (U) and plutonium (Pu) are extracted into the organic phase by nitrate and TBP complexation while the various fission products remain in the initial aqueous phase. Pu is then chemically reduced to its trivalent state and back-extracted into a second aqueous phase, thereby separating the two fissile materials. …

Development Of Mixed O/S-Donor Imidazole Thione Ligands For Trivalent Lanthanide/Actinide Separations, Rhianna Wolsleger

All Dissertations

Separation of lanthanides and actinides is difficult due to their very similar size and charge. Increasing selectivity for actinides over lanthanides is possible by incorporating a softer, more polarizable donor atom into a chelating ligand, since the softer donor atom is capable of greater orbital overlap with the 5f orbitals of the actinides vs the 4f orbitals of the lanthanides. Sulfur-containing imidazole thione chelating ligands have not been investigated for this purpose but possess a resonance structure that puts significant negative charge on the sulfur, enabling it to form strong metal-sulfur bonds compared to other sulfur-containing ligands such as thioethers …

Intrinsic Gas-Phase Behavior Of Uranium Species: A Comprehensive Reactivity Study Of [O=U≡Ch]+ And [Uh]+, Justin Terhorst

Electronic Theses and Dissertations

The intrinsic chemistry of actinide elements, particularly uranium, remains a key challenge in understanding f-block reactivity due to the complexity introduced by solvent interactions, counter-ions, and complex equilibria in the condensed phase. In this dissertation, a systematic gas-phase study utilizing preparative tandem ion-trap mass spectrometry (PTMSⁿ) is presented, focusing on the reactivity of uranium-centered species, specifically [OUCH]⁺, an oxy uranium methylidyne species, and [UH]⁺ ions. By stripping away solvent effects and isolating the ions, PTMSⁿ provides a powerful platform to probe the fundamental chemical behavior of uranium species in their intrinsic state.

The …

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 …

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 …

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 …

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 …

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 …

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 …

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 …

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 …

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 …

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 …

Optimization Of The Microprecipitation Procedure For Nuclear Forensics Applications, Lyndsey Renee Kelly

UNLV Theses, Dissertations, Professional Papers, and Capstones

Microprecipitation has become one of the most widely used sample preparation techniques for alpha spectroscopy. Many factors during the precipitation process can affect the yield and energy resolution by adding unwanted mass to the sample. Current applications in nuclear forensics call for an optimization of energy resolution and yield in order to improve identification and quantify specific radionuclides. The purpose of this research is to determine the optimal parameters used for microprecipitation. The optimal solution temperature, precipitation time, carrier amount, and hydrofluoric acid amount are used to investigate the influence of varying the type of carrier, as well as, the …

Fundamental Chemistry Of U And Pu In The Tbp-Dodecane-Nitric Acid System, Kenneth Czerwinski

Separations Campaign (TRP)

The research objective is to experimentally evaluate the fundamental speciation of Pu and U in the TBP-dodecane-nitric acid- AHA system and the effect of pertechnetate, specifically:

• To determine the influence of nitrate on the speciation of U and Pu in the TBP-dodecane-nitric acid system. The aqueous and organic speciation of U and Pu are examined as a function of the nitric acid concentration, nitrate concentration, actinide ion concentration, temperature, and time.

• To determine the speciation of U and Pu with AHA in the presence and absence of TBP-dodecane organic phase. The aqueous and organic speciation of U and …

Evaluation Of Fundamental Radionuclide Extraction Data For Urex, Kenneth Czerwinski

Separations Campaign (TRP)

The speciation of technetium and actinides in advanced solvent extraction systems is the basis for their manipulation in separations. The ability to understand and predict radionuclide speciation is paramount to successful modeling of proposed separation systems. This project will examine the speciation of radionuclides in different stages of the uranium extraction (UREX) separation scheme, providing data useful to modeling. The areas to be examined include the speciation of uranium and plutonium with tributylphosphate and the kinetics and thermodynamics of lanthanides and actinides in the TALSPEAK (Trivalent actinide lanthanide separation by phosphorous reagent extraction from aqueous complexes) system. The complexation constants …

Fundamental Chemistry Of U And Pu In The Tbp-Dodecane-Nitric Acid System, Kenneth Czerwinski

Separations Campaign (TRP)

The research objective is to experimentally evaluate the fundamental speciation of Pu and U in the TBP-dodecane-nitric acid- AHA system and the effect of pertechnetate, specifically:

To determine the influence of nitrate on the speciation of U and Pu in the TBP-dodecane-nitric acid system. The aqueous and organic speciation of U and Pu are examined as a function of the nitric acid concentration, nitrate concentration, actinide ion concentration, temperature, and time.

To determine the speciation of U and Pu with AHA in the presence and absence of TBP-dodecane organic phase. The aqueous and organic speciation of U and Pu are …

Fundamental Chemistry Of U And Pu In The Tbp-Dodecane-Nitric Acid System, Kenneth Czerwinski, Byron Bennett

Separations Campaign (TRP)

The research objectives of this project are as follows:

• To determine the influence of nitrate on the speciation of U and Pu in the TBP-dodecane-nitric acid system. The aqueous and organic speciation of U and Pu are examined as a function of the nitric acid concentration, nitrate concentration (by the addition of NaNO₃), actinide ion concentration, temperature, and time.
• To determine the speciation of U and Pu with AHA in the presence and absence of TBP-dodecane organic phase. The aqueous and organic speciation of U and Pu are evaluated as a function of AHA concentration, metal ion concentration, …

Electrochemical Separation Of Curium And Americium, David W. Hatchett, Kenneth Czerwinski

Separations Campaign (TRP)

The objective of this project is to develop a method for the separation of Am from Cm based on electrochemical techniques. Electrochemical systems that allow the thermodynamics of actinide and lanthanide complexes to be systematically evaluated and tuned will be examined. The influence of complex formation on the ability to selectively isolate a given species electrochemically will be evaluated. Metal-ligand complex formation provides a useful derivation technique to increase solubility in solution environments that favor precipitation. In addition, the thermodynamic properties of a complex relative to the isolated species may be shifted to more suitably measurable electrochemical separation regimes. Electrochemical …

Fundamental Chemistry Of U And Pu In The Tbp-Dodecane-Nitric Acid System, Kenneth Czerwinski, Byron Bennett

Separations Campaign (TRP)

The speciation of hexavalent U and tetravalent Pu will be examined in the TBP-dodecane-nitric acid systems. This topic is chosen based on data needs for separation modeling identified by the AFCI. Emphasis will be placed on studying the influence of nitrate and acetohydroxamic acid on U and Pu speciation as well as conditions where a third phase forms in the organic phase. The organic phase will be 30% TBP in dodecane. Equal volumes of aqueous and organic phase will be used. The speciation of the actinides in the aqueous and organic phase will be determined by a number of different …