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Smith, Frances N.

Publications and source records attributed to Smith, Frances N..

8 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Calcium carbonate minerals as scavengers of metals and radionuclides: Their role in natural attenuation and remediation

Calcium carbonates (CaCO3) are ubiquitous naturally occurring minerals in subsurface sediments. Calcium carbonate coatings are common in many terrestrial environments and are known to coat a variety of reactive mineral surfaces in soils and sediments, altering their reactivity and chemical behavior. For these reasons, contaminant interactions with CaCO3 minerals are relevant to contaminant fate and transport. Significant advancements have been made recently toward identifying relevant contaminant (e.g., U, I, and Cr) attenuation mechanisms, which may also serve as a basis for in situ remediation strategies. Hence, the objective of this review paper is to 1) describe the state-of-knowledge of calcium carbonate minerals as universal scavengers of metals and radionuclides; 2) provide a state of the science of how calcium carbonate interactions affect contaminant fate and transport in the subsurface environmental systems; and 2) provide insights on the use of calcium carbonate natural attenuation mechanisms and their application to the remediation of complex sites. Knowledge gaps are also identified that, when closed, can advance the use of carbonate minerals for in situ remedy applications.

Qafoku, Nikolla↗
DOE OSTI2021

Thermal properties of U-Mo alloys irradiated under high fission power density

A variety of physical and thermal property measurements made on irradiated U-Mo alloy monolithic fuel samples with a Zr diffusion barrier and clad in Al alloy 6061 are reported. These properties form the basis for additional investigations in thermal behavior of U-Mo fuel under high performance research reactor irradiation conditions. Measurements were performed on samples harvested from fuel plates irradiated under high fission power density and surface heat flux and complement previous measurements on samples subjected to moderate fission power density and surface heat flux. Specific heat capacity of irradiated monolithic U-Mo increases with increasing temperature and fission density, but carries large uncertainties associated with thickness measurements used to determine the mass fraction of the layer constituents for extraction of the U-Mo specific heat capacity, specifically the very thin and nonuniform Zr diffusion barrier. Density of irradiated monolithic U-Mo decreases with increasing fission density resulting from fission gas swelling and porosity formation. Thermal diffusivity of irradiated monolithic U-Mo increased with increasing temperature and decreased with increasing fission density. Thermal conductivity of irradiated monolithic U-Mo increased with increasing temperature, and in general, appeared to decrease and become less sensitive to temperature with increasing fission density. Thermal conductivity measurements compared to a semi-empirical model agreed within ±30%. It is suspected that the main driver in deviation between model calculations and measurements is the fission gas swelling determination, which does not account for fission power density or irradiation temperature.

uranium (U), molybdenum, nuclear fuel, thermal con↗
DOE OSTI2018

A Workshop on the History of Plutonium Processing at Hanford Washington as the Foundation for Modern-day Plutonium Process Science

Numerous national laboratories in the United States have roots related to the Manhattan Project that contributed to the end of World War II. The pioneering science and engineering that took place over the decades that followed continues to influence modern-day actinide-related research at those institutions, leading to unique strengths and cutting-edge ideas and perspectives. These same national laboratories also face a challenge: figuring out how to capture the expertise of a retiring workforce who had first-hand experience in these pioneering nuclear efforts. Recently, at PNNL a “Train-the-Trainer” approach has been piloted where mentors and mentees are paired together to develop and deliver interactive workshops on historical topics that relate to modern-day research, such as Plutonium Processing or Environmental Management of Legacy Nuclear Waste. This approach was used to develop a workshop that beings with the Historic Hanford process plutonium chemistry and engineering, describes its influence on current plutonium separation and process science, and then details the chemistry of plutonium as it progresses from a minor constituent in irradiated fuel to purified solid product. This workshop is targeted to the practitioner of applied science and technology wishing to gain a better understanding of the history and process-related chemistry of element 94 so that they may better direct the tools of their specific craft toward the present and future needs of plutonium science.

Smith, Frances N.↗
DOE OSTI2018

Incorporation Modes of Iodate in Calcite

Iodate incorporation in calcite is a potential sequestration pathway for environmental remediation of radioiodine-contaminated sites (e.g., Hanford Site, WA), but the mechanisms of iodate incorporation are still unknown. Molecular dynamics simulations were performed to determine the local coordination environment, the associated charge compensation schemes, and the tendency for iodate to segregate at calcite surfaces. Charge compensation by substitution of a calcium ion by either a sodium ion or a proton (i.e., the effect of pH), was considered. For charge compensation by sodium ions, a nearest-neighbor position was determined to be energetically favored, whereas for charge compensation by protons, the HIO3 molecule was found to be metastable and the formation of a bicarbonate ion was energetically favored. The iodate ion also showed a preference for the topmost atomic layer of the (104) calcite surface, which dominates the morphology of calcite crystals. Simulated trajectories were used to calculate iodine K-edge extended X-ray absorption fine structure spectra, which matched experimental data of iodate co-precipitated with calcite. The best-fit combination consisted of a significant proportion of surface-segregated iodate ions and included charge compensation by both sodium ions and protons. Therefore, an important implication is that the iodate accumulated at the surface regions of calcite crystals, may undergo mobilization under conditions that promote calcite dissolution. In addition, surface area and pH of the surrounding solution are both expected to strongly affect the extent of iodate incorporation in calcite. Hence, calcite-based iodate remediation strategies need to consider these impacts.

Kerisit, Sebastien N.↗
DOE OSTI2017

Importance of interlayer H bonding structure to the stability of layered minerals

Layered (oxy) hydroxide minerals often possess out-of-plane hydrogen atoms that form hydrogen bonding networks which stabilize the layered structure. However, less is known about how the ordering of these bonds affects the structural stability and solubility of these minerals. Here, we report a new strategy that uses the focused electron beam to probe the effect of differences in hydrogen bonding networks on mineral solubility. In this regard, the dissolution behavior of boehmite (γ-AlOOH) and gibbsite (γ-Al(OH)3) were compared and contrasted in real time via liquid cell electron microscopy. Under identical such conditions, 2D-nanosheets of boehmite (γ-AlOOH) exfoliated from the bulk and then rapidly dissolved, whereas gibbsite was stable. Further, substitution of only 1% Fe(III) for Al(III) in the structure of boehmite inhibited delamination and dissolution. Factors such as pH, radiolytic species, and knock on damage were systematically studied and eliminated as proximal causes for boehmite dissolution. Instead, the creation of electron/hole pairs was considered to be the mechanism that drove dissolution. The widely disparate behaviors of boehmite, gibbsite, and Fe-doped boehmite are discussed in the context of differences in the OH bond strengths, hydrogen bonding networks, and the presence or absence of electron/hole recombination centers.

58 GEOSCIENCES↗
DOE OSTI2017

Conceptual Model of Iodine Behavior in the Subsurface at the Hanford Site

Isotopes of iodine were generated during plutonium production within the nine production reactors at the U.S. Department of Energy Hanford Site. The short half-life 131I that was released from the fuel into the atmosphere during the dissolution process (when the fuel was dissolved) in the Hanford Site 200 Area is no longer present at concentrations of concern in the environment. The long half-life 129I generated at the Hanford Site during reactor operations was (1) stored in single-shell and double-shell tanks, (2) discharged to liquid disposal sites (e.g., cribs and trenches), (3) released to the atmosphere during fuel reprocessing operations, or (4) captured by off-gas absorbent devices (silver reactors) at chemical separations plants (PUREX, B-Plant, T-Plant, and REDOX). Releases of 129I to the subsurface have resulted in several large, though dilute, plumes in the groundwater. There is also 129I remaining in the vadose zone beneath disposal or leak locations. The fate and transport of 129I in the environment and potential remediation technologies are currently being studied as part of environmental remediation activities at the Hanford Site. A conceptual model describing the nature and extent of subsurface contamination, factors that control plume behavior, and factors relevant to potential remediation processes is needed to support environmental remedy decisions. Because 129I is an uncommon contaminant, relevant remediation experience and scientific literature are limited. In addition, its behavior in subsurface is different from that of other more common and important contaminants (e.g., U, Cr and Tc) in terms of sorption (adsorption and precipitation), and aqueous phase species transformation via redox reactions. Thus, the conceptual model also needs to both describe known contaminant and biogeochemical process information and identify aspects about which additional information is needed to effectively support remedy decisions.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2017

Developing methodologies for source attribution: glass phase separation in Trinitite using NF3

This study details thermal reactions between glasses, common minerals, and Trinitite post-detonation material with the fluorinating agent nitrogen trifluoride (NF3). The ultimate goal of our investigation is to develop a relatively rapid method for the effective separation of bomb components from complex matrices resulting from a nuclear explosion. Trinitite samples, silicate minerals (quartz; plagioclase and microcline), amorphous SiO2, calcite, a natural glass (obsidian), and two synthetic glasses were characterized extensively before and after the fluorination to fully understand the effects of the NF3 thermal treatment. Samples were reacted with NF3 using a combined thermogravimetric (TG) differential thermal analysis (DTA) unit, as well as in a stainless steel bomb reactor connected to a fluorination line. Subsequent to the NF3 treatment, samples were imaged by scanning electron microscopy in order to document changes in grain size and morphology.

Koeman, Elizabeth C.↗