Physical Sciences and Mathematics Commons^™

Ligand-Promoted Dissolution Of Uranyl Phosphate Across Scales, Brennan Ferguson

All Dissertations

The formation of uranyl phosphate precipitate is a remediation strategy because the low solubility of uranyl phosphate minerals, like chernikovite, limits the mobility of uranium in contaminated soils. However, organic ligands can complex with aqueous metal cations to form more soluble species. For example, citrate is a commonly occurring organic ligand produced by plants and microbes that increases the solubility of uranium and therefore the dissolution of uranyl phosphate minerals in the uranyl phosphate-citrate system. This effect is an important control on the mobility of uranium in organic-rich, and near-surface vegetated environments. Nevertheless, key aspects of the citrate-uranyl phosphate system …

Immobilization Of Uranium And Iodine By Calcium Phosphate Minerals, Angel L. Jimenez-Arroyo

Theses and Dissertations

This dissertation is comprised of three independent but interconnected studies with the scope of further understanding uranium and iodine partitioning between apatite and fluid. The studies herein presented investigated: 1) brushite to apatite crystallization method; 2) the degree of uranium incorporation into apatite; 3) the degree of iodine incorporation into apatite. The importance of this work is assessing the role of apatite in immobilizing these elements, where uranium is a major component of spent nuclear fuel and iodine is a chemical analog of its radioactive isotope (¹²⁹I). Once we understand the incorporation mechanisms, we will provide data that …

Rock-Fluid Interaction And The Incorporation Of Cations Into Calcite During Recrystallization In Multiple Hydrothermal Systems., Van Anh Nguyen

Theses and Dissertations

Fluid-rock interaction causes an exchange of isotopes or elements through various reactions. The rate of these reactions strongly depends on temperature. The interaction involves dissolution precipitation, chemical exchange reactions, redox reactions, diffusion, and their combinations. The goal of studying fluid-rock interaction is to understand the change in mineral chemistry of the rock materials when in contact with an aqueous solution. These processes occur in all regions of the Earth where aqueous solutions are found. This work is comprised of three independent studies which provide an understanding about crystallization processes under multiple hydrothermal conditions with geological and environmental applications.

In the …

Wetland Uranium Transport Via Iron-Organic Matter Flocs And Hyporheic Exchange, Connor J. Parker

All Dissertations

Uranium (U) released from the M-Area at the Department of Energy Savannah River Site into Tims Branch, a seasonal wetland and braided stream system, is estimated to be 43,500 kg between 1965 and 1984. The motivation for this work is the uranium’s persistence in the wetland for decades, where it is estimated that 80% of the U currently remains in the Tims Branch wetland. U has begun to incorporate into wetland iron (Fe) and carbon cycles, associating with local Fe mineralogy and deposits of rich wetland organic matter (OM). The objective of this work is to characterize the chemical phases …

Understanding The Chemical Weathering Rate And Element Mobility Of Soils: Using U-Series, Nd-Sr Isotopes Ree And Quantum Chemistry Computational Simulation, Jiye Guo

Open Access Theses & Dissertations

Soil played as the central role in the interaction of biosphere, hydrosphere, lithosphere and atmosphere and is the heart of earth's critical zone study. The weathering and element mobility of soils have drawn considerable attention in soil studies since the complexity of these processes and the critical influence towards the earth and humanity, e.g., the global carbon cycles and fertilization. However, the interaction between soils and various factors including precipitation, bedrock ages, altitude is not well understood. Basse-Terre Island at French Guadeloupe, a small volcanic tropical island that has steep environmental gradients of bedrock ages, topography and precipitation, can be …

Interaction Of Aqueous U(Vi) With Goethite, Montmorillonite, And Uo2(S), Anshuman Satpathy

McKelvey School of Engineering Theses & Dissertations

Uranium contamination in subsurface environments is a matter of great concern throughout the world. Fate and transport of uranium in the subsurface can be controlled by U(VI) adsorption and reduction onto common iron (oxy)hydroxides and clay minerals. Aqueous U(VI) can also exchange uranium atoms with solids comprised of uranium which can potentially lead to changes in the morphology of the uranium-containing solids and affect their stability. First, the performance of multiple surface complexation models (SCMs) on adsorption of U(VI) onto goethite was analyzed for a broad range of input conditions. Individual models could fit the data for which they were …

Investigating The Impact Of Meteoric Diagenesis On The Geochemistry Of Carbonate Eolianites, Eleuthera And Water Cay, The Bahamas, Graham S. Bonnot

LSU Master's Theses

The geochemical signatures imparted in major, minor, and trace elements, combined with light isotopes, suggest promising applications regarding the stabilization of meteorically altered limestone eolianites. Previous high-resolution studies have indicated that elements associated with carbonate diagenesis such as Mg and Sr can be valuable proxies for salinity and aragonite dissolution, respectively. In addition to testing these proxies, the analyses of several temperature-, diagenetic-, bioactive-, and redox-sensitive elements were evaluated using laser ablation inductively-coupled plasma mass spectrometry (LA-ICP-MS) to identify additional indicators during carbonate diagenesis. Two geochemical drivers of U were identified; (1) aragonite dissolution similar to Sr and (2) oxidation …

Raman Spectroscopic Investigation Of The Speciation Of Uranyl (Vi) And Thorium (Iv) Ions In Chloride-Bearing Aqueous Solutions Under Hydrothermal Conditions, Nadib Akram

MSU Graduate Theses

Raman spectra were acquired for a uranyl chloride aqueous solution at temperatures ranging from 25°C to 500°C at the chloride concentration of 6M and uranium (vi) concentration of 0.05M. The measurements were taken by sealing the sample in a hydrothermal diamond anvil cell (HDAC) which enabled spectra acquisition at non-ambient conditions. The pressure inside the cell was measured by estimating the liquid-vapor homogenization temperature (T_H) and using the isochoric equation of state diagram of water. The acquired spectra were then fitted to determine the speciation distribution of the various uranyl chloride species for the mentioned concentration. The developed …

Improving Thorium-230 Determination In Marine Sediment, Katherine Mateos

Independent Study Project (ISP) Collection

Our oceans are intimately related to the climate of our planet. Paleoceanographic approaches aim to study oceans through geologic time to improve models of future climate. Radioisotopes provide us with chemical tracers that help us understand change through time. The uraniumseries decay chain contains thorium-230, a decay product of uranium-234. This isotope is useful to paleoceanographers in its disequilibrium to its parent isotope and in determining the flux of sediment falling to the ocean floor. In order to use 230Th to study oceans, we must be able to accurately measure the amount of thorium in sediment samples. Thorium is found …

Use Of Sodium Dithionite For Groundwater Restoration Following Uranium In-Situ Recovery Mining At The Smith Ranch-Highalnd Site In Wyoming, Rose J. Harris

Earth and Planetary Sciences ETDs

Uranium in-situ recovery (ISR) is a subsurface aqueous mining technique used to extract uranium from sandstone roll-front deposits. After ISR mining, groundwater restoration is conducted to decrease concentrations of residual U(VI) and other contaminants leftover in the groundwater. Sodium dithionite, a strong chemical reductant, is being tested for use in groundwater restoration following uranium ISR at the Smith Ranch-Highland site in Wyoming. Sodium dithionite has been used to remediate chromium plumes by creating an in-situ permeable reactive barrier, but there has been no work using sodium dithionite for groundwater restoration following uranium ISR mining.

Laboratory batch and column experiments, and …

Investigating Uranium Incorporation In Modern Carbonates By Sequential Extraction: Applied To The Permian - Triassic Boundary In Lung Cam, Vietnam, Christopher Michael Wray

LSU Master's Theses

The Uranium (U) isotopic system can be used to model the extent of global-scale ocean anoxia by utilizing the 238U/235U ratios as a paleo-redox indicator (δ238U). While recent studies have shown promise with the use of this novel proxy, variability is seen in modern carbonate sediment samples suggesting that more work is needed in order to understand elemental U uptake during early marine diagenesis. This thesis utilizes a sequential extraction methodology in order to understand the distribution of authigenic U within carbonate sediments.

This thesis consists of four parts, (1) an evaluation and modification of a sequential extraction methodology for …

Abrupt Ocean Anoxia During The Late Ordovician Mass Extinction Detected Using Uranium Isotopes Of Marine Carbonates, Rickey Bartlett, Maya Elrick, Yemane Asmerom, Viorel Atudorei

Earth and Planetary Sciences ETDs

The Ordovician witnessed an explosion in marine biodiversity punctuated by the first of the ‘big-5’ Phanerozoic mass extinctions, the Late Ordovician mass extinction (LOME). The LOME consists of two discrete pulses occurring at the beginning and end of the Hirnantian. Lithologic and geochemical evidence suggests widespread marine anoxia triggered the second LOME pulse; however, most of these redox proxies record local bottom water or porewater conditions rather than global seawater conditions. To evaluate global redox trends, we utilize uranium (U) isotopes and trace element geochemistry of marine carbonates as a global marine redox proxy.

Bulk carbonate samples were collected from …

Using Bromide Tracer To Measure Uranium Diffusivity In Ground Water Sediments, Francis Michael Tee, Morris E. Jones, Megan K. Dustin, Sharon Bone, John Bargar

STAR Program Research Presentations

More than 129 million liters of groundwater are contaminated with uranium at Old Rifle, Colorado – a former uranium-processing site that operated until 1958. The original Department of Energy (DOE) strategy for remediation, involving natural flushing of U from the groundwater through mixing with surface water, has not proven successful. Thin pockets of silt-, clay-, and organic-rich sediments referred to as naturally reduced zones (NRZs) act both as sinks and sources of U to the aquifer, contribute to plume persistence, and appear to be diffusion limited controlled.

To better understand how the NRZs are diffusion limited controlled, a bromide tracer …

Modeling Background Radiation Using Geochemical Data, Kara Marsac

UNLV Theses, Dissertations, Professional Papers, and Capstones

Aerial gamma ray surveys have many applications in geology and science in general, such as locating mining prospects, defining radioactive plumes, and detecting nuclear weapons. Unfortunately there is currently no simple way to separate the natural gamma radiation of soil and rocks from that of contaminants such as radioactive plumes. This project used geochemical data (uranium, potassium and thorium concentrations) collected from national databases, private companies, and the NURE (National Uranium Resource Evaluation) Survey, to create forward models of exposure rates measured by aerial gamma ray surveys. We developed these techniques using an area in north central Arizona known as …

Spectroscopic Study Of Uranium (Vi) Reduction By Plant Biomass, Margaret C. Murphy, John Bargar, Noémie Janot

STAR Program Research Presentations

Uranium is a common and problematic groundwater contaminant at Department of Energy legacy sites. At the former uranium ore processing plant at Rifle, Colorado, sediments rich in decayed plant biomass contain large concentrations of uranium that are slowly being released back to the aquifer. To simulate the reaction that occurs in organic rich sediments of the Rifle aquifer, biomass was incubated in U (VI) bearing groundwater. Carbon X-ray absorption spectroscopy (XAS) was then used to measure if uranium was bound to the biomass. When uranium binds to biomass the peaks in the C XAS spectra will change shape. Uranium L …

The Effects Of Changes In Water Content On Uranium(Vi) Leaching In Sediment Mixtures Containing Gravel, Andrew Weber Moore

Masters Theses

This study is aimed at understanding the physical and chemical effects that changes in water content have on uranium leaching in sediment containing gravel. It was hypothesized that leaching will be more efficient under unsaturated conditions because flow will be restricted to the smallest pores and will have the most contact with the uranium contaminated sediment. Under saturated conditions, a large portion of the flow will bypass the < 2 mm material, and in turn not come into contact with uranium contaminated material. Batch adsorption and desorption experiments were performed on < 2 mm ERDF sediment to determine the linearity and reversibility of sorption processes and to aid in the interpretation of the leaching experiments. Results of the desorption experiments on aged, contaminated sediments show that the mass percent of sorbed U(VI) released to solution decreased as the sorbed concentration of U(VI) decreased. The opposite trend was observed on freshly contaminated sediments. This indicated that aging increased U(VI) affinity for the solid phase and was attributed to either the crystallization of calcite, which incorporated a portion of the sorbed U(VI) as it crystallized, or the presence of voids in basaltic lithic fragments accessed by diffusion. Column leaching experiments were performed at two water contents on artificially contaminated sediment collected from the Department of Energy’s (DOE) Hanford Site, Washington state. The sediment contained 81.3% gravel (> 2 mm) by mass. Non-reactive tracers were well fit with the convection-dispersion equation (CDE) at both high and low water contents indicating physical equilibrium. The column experimental data were fitted to an …

The Speciation Of Dissolved Uranium In Marine Waters, Darrin Kent Mann

OES Theses and Dissertations

Uranium has been used extensively for quantifying geochemical processes in the marine environment. Due to its low concentration, about 3.3 μg/1, some form of preconcentration is required for analysis. The two most widely used pre-concentration schemes are co-precipitation with iron hydroxide, and chelating ion exchange chromatography. These methods were developed by following the behavior of inorganic uranium isotopes and seemed to give identical results. However, when used for trace metal analysis, these methods have been shown to extract different fractions from the same sample. Chelex-100 resin removes only inorganic or weakly bound trace metals from a solution, while the precipitates …