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Decontamination of uranium contaminated metals - 15 years of experience - 15528

Uranium contaminated waste is somewhat of a special case among radioactive waste as the uranium, if enriched, also is a valuable asset. Incineration and pyrolysis of uranium contaminated dry active waste (DAW) was covered during WM'14. Uranium contaminated metals is however somewhat different when it comes treatment and recovery of uranium. Since the late 1990's the Metals Treatment and Recycling Facility in Studsvik Sweden has treated approximately 1500 tonnes of metals contaminated by uranium. Depending on the metal, melt-decontamination may or may not be a way of salvaging metals if the pre-treatment was not enough. The only metals that currently are subject to melt decontamination are iron based materials as well as lead. Other metals such as aluminium, brass and copper must all be cleaned prior to melting. Recovery of uranium from the secondary waste is most likely economically feasible only from the first step, the pre-melting decontamination, as the slag is just that, a slag, which is molten at a high temperature, and thereafter cooled under non-controlled conditions so uranium is trapped inside in an unspecified chemical form. This paper will describes experiences and lessons learned from 15 years of treatment, including melt-decontamination, of uranium contaminated metals. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Stability of a Uranium-Contaminated Plume in a Karst Aquifer in Northwest New Mexico - 19574

The US Department of Energy (DOE) Office of Legacy Management monitors groundwater contamination resulting from ore processing operations conducted between 1953 and 1982 at a former uranium mill site on property that is now part of the Bluewater, New Mexico, Disposal Site. The site is located in the Grants Mineral Belt in northwest New Mexico at the base of the Zuni Mountains. It is estimated that prior to mill tailings encapsulation in 1995, approximately 21.6 billion liters (5.7 billion gallons) of tailings fluid seeped from the main tailings impoundment into the underlying aquifers. Today, there is remnant groundwater contamination from the mill in two aquifers: the San Andres-Glorieta (SAG) bedrock aquifer and the Ancestral Rio San Jose alluvial aquifer. Groundwater contamination in the SAG aquifer is of particular concern, as the aquifer is the primary water source in the region for municipal, agricultural, and industrial use. Municipal wells for the region are located as close as 6.4 kilometers (4 miles) southeast of the Main Tailings Disposal Cell. The SAG uranium plume extends east for more than 4.8 kilometers (3 miles) beyond the site's eastern boundary, along the direction of groundwater flow. The plume intersects the Homestake Mining Company site, another former uranium mill site undergoing active remediation. The SAG aquifer contains two formations, the Lower Permian San Andres Limestone and the Glorieta Sandstone. Most of the groundwater moving through the SAG aquifer is in ancient karst features consisting of open conduits where the limestone has dissolved, resulting in flow through solution cavities, solution channels, cavernous zones, and enlarged fracture openings. These features make the San Andres Limestone extremely permeable and capable of rapidly transporting groundwater. In addition, the karst characteristics make the aquifer difficult to evaluate and the uranium plume difficult to characterize. Numerous faults in the area, including two directly under the Main Tailings Disposal Cell, further complicate characterization by impacting groundwater flow both onsite and in the vicinity. A DOE study of the SAG aquifer uranium plume at the Bluewater site, conducted in 2014, indicated that the plume had moved offsite soon after the start of milling and effectively stabilized in its present location prior to the 1980's. An updated study completed in 2018 confirmed previous information regarding general plume stability and provided insight regarding potential localized trends east and south of the Main Tailings Disposal Cell. One such trend may be decreasing uranium concentrations east of the Main Tailings Disposal Cell, potentially attributable to regional groundwater elevation decreases. Both the 2013 and 2017 plumes suggest that the dissolved uranium contamination is derived from the leaching of a secondary mineralized zone derived from seeped tailings fluids in the geologic formations and fault zones below the Main Tailings Disposal Cell at the Bluewater site. In developing the 2013 and 2017 SAG aquifer uranium plume depictions, DOE had to address challenges associated with data quality and comparability. Analytical results used to determine the plume extent were compiled from multiple sources, including the state of New Mexico, Homestake Mining Company, and DOE. Each source used different well identifiers and coordinate systems, and well information between sources was inconsistent. Also, the integrity of some wells was questionable and necessitated review; casing integrity was found to be compromised in multiple wells. Given these uncertainties, some of these wells were excluded from the characterization. Another source of uncertainty is the paucity of wells, particularly monitoring wells, near or immediately downgradient of the leading edge of the plume. Therefore, the exact extent of the SAG aquifer uranium plume is not known at this time. There is, however, no evidence or indication of milling-related contamination in municipal wells. Furthermore, due to plume stability and direction of groundwater flow, the municipal wells are not expected to be impacted. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Uranium Release from Acidic Weathered Hanford Sediments: Single-Pass Flow-Through and Column Experiments

The reaction of acidic radioactive waste with sediments can induce mineral transformation reactions that, in turn, control contaminant fate. Here, sediment weathering by synthetic uranium-containing acid solutions was investigated using bench-scale experiments to simulate waste disposal conditions at Hanford’s cribs, USA. During acid weathering, the presence of phosphate exerted a strong influence over uranium mineralogy and a rapidly precipitated, crystalline uranium phosphate phase (meta-ankoleite [K(UO2)(PO4)·3H2O]) was identified using spectroscopic and diffraction-based techniques. In phosphate-free system, uranium oxyhydroxide minerals such as K-compreignacite [K2(UO2)6O4(OH)6·7H2O] were formed. Single-pass flow-through (SPFT) and column leaching experiments using synthetic Hanford pore water showed that uranium precipitated as meta-ankoleite during acid weathering was strongly retained in the sediments, with an average release rate of 2.67E-12 mol g-1 s-1. In the absence of phosphate, uranium release was controlled by dissolution of uranium oxyhydroxide (compreignacite-type) mineral with a release rate of 1.05-2.42E-10 mol g-1 s-1. The uranium mineralogy and release rates determined for both systems in this study support the development of accurate U-release models for prediction of contaminant transport. These results suggest that phosphate minerals may be a good candidate for uranium remediation approaches at contaminated sites.

54 ENVIRONMENTAL SCIENCES↗

The Impact of Coordination Environment on the Thermodynamic Stability of Uranium Oxides

Amorphous uranium oxides are acknowledged to arise via industrial processes relevant to the nuclear fuel cycle yet evade rigorous structural characterization. An encouraging approach is to develop statistical relationships between uranium–oxygen coordination environments and thermodynamic stability from which general statements about the likelihood of observing particular U–O arrangements can be made. The number of known crystalline uranium oxides is insufficient to build statistical relationships. We have developed a database of theoretical compounds using genetic algorithms with the density functional theory as a foundation to analyze coordination geometries in the uranium–oxygen phase space. We draw fundamental insights into the nature of uranium–oxygen interactions by correlating total energy with the coordination environment. The most stable configuration of U cations with O anions is in an environment with coordination numbers 5–8 in a cubic configuration. Higher and lower coordination numbers are observed only in metastable phases. General trends are observable in the relationships between the coordination number, density, and uranium fraction in each structure. The new insight into uranium coordination enabled by these analyses is foundational for further studies into the characteristic properties of individual uranium oxide materials and for elucidation of potential oxidation pathways for uranium metal.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Uranium carbonate complexes demonstrate drastic decrease in stability at elevated temperatures

Quantitative understanding of uranium transport by high temperature fluids is crucial for confident assessment of its migration in a number of natural and artificially induced contexts, such as hydrothermal uranium ore deposits and nuclear waste stored in geological repositories. An additional recent and atypical context would be the seawater inundated fuel of the Fukushima Daiichi Nuclear Power Plant. Given its wide applicability, understanding uranium transport will be useful regardless of whether nuclear power finds increased or decreased adoption in the future. The amount of uranium that can be carried by geofluids is enhanced by the formation of complexes with inorganic ligands. Carbonate has long been touted as a critical transporting ligand for uranium in both ore deposit and waste repository contexts. However, this paradigm has only been supported by experiments conducted at ambient conditions. We have experimentally evaluated the ability of carbonate-bearing fluids to dissolve (and therefore transport) uranium at high temperature, and discovered that in fact, at temperatures above 100 °C, carbonate becomes almost completely irrelevant as a transporting ligand. This demands a re-evaluation of a number of hydrothermal uranium transport models, as carbonate can no longer be considered key to the formation of uranium ore deposits or as an enabler of uranium transport from nuclear waste repositories at elevated temperatures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

In vitro toxicity assessment of uranium particulates on different human lung epithelial cell models

Inhalation of uranium aerosols produced via human activities such as mining can pose a threat to human respiratory systems. Uranium oxide particulates emit short-range alpha particles that elicit DNA and direct damage, beyond associated physiochemical heavy-metal toxicity, to internal epithelial tissues. The availability of reliable in vitro models to study radiation exposure can greatly enhance our ability to understand and combat the biological impacts of exposure. However, the toxicological effects of alpha emissions and/or the oxidation states of uranium particulates vary across different human lung epithelial cell models and have not been systematically compared. We have endeavored to address this limitation by comparing impacts in three different human lung cell models: primary human bronchial and tracheal epithelial cells, primary human small airway epithelial cells, and human adenocarcinoma alveolar basal epithelial cells. Other studies have mainly investigated the toxicity of depleted uranium. Here, we compared the exposure of uranium oxide particulates (U 3 O 8 and UO 3 ) of different enrichment states on the chosen cell systems. Each cell model was exposed to 0.1, 1, 10, 50, 100, and 500 µg/mL of depleted U 3 O 8 , highly-enriched U 3 O 8 , and natural UO 3 particulates for 24 hours in submerged monolayer cultures. We compared viability and superoxide dismutase activity results across cell lines and uranium enrichment/ oxidative states. The results showed that 1) the oxide state of the particulates affected cell viability, implying that uranium’s different oxidation states contribute to different toxicological responses, and 2) each cell model reacts differently when exposed to uranium oxides, which may provide insights into the mechanistic processes associated with the exposure of radiological particulates on different biological systems. For instance, increased uranium enrichment corresponds to increased toxicity for the primary cells, but not for the immortalized cells. Our study shows that a holistic approach that incorporates similarities between model systems and types of radionuclides is required to truly develop empirical solutions for radiation exposure.

59 BASIC BIOLOGICAL SCIENCES↗

Evaluation of the Change in Uranium Mobility in Sediments from the Hanford 300-FF-5 Stage B Polyphosphate Field Injection

The purpose of this study was to evaluate the change in uranium mobility in the periodically re-wetted zone (PRZ) and upper unconfined aquifer of the Hanford Site’s 300-FF-5 operable unit as a result of Stage B polyphosphate (PO 4 ) injections. These 300 Area sediments are beneath or near the former North Process Pond, which has previously been shown to contain metatorbernite [Cu(UO 2 ) 2 (PO 4 ) 2 •8H 2 O] and uranophane [Ca(UO 2 ) 2 (SiO 3 OH) 2 •5H 2 O], along with aqueous and adsorbed uranium (U), and small amounts of U in calcite as a result of acidic disposal with a significant number of co-contaminants. Previous laboratory-scale studies have identified multiple mechanisms that decrease uranium mobility with polyphosphate injection: (a) precipitation of a low-solubility uranium-phosphate mineral (autunite); (b) precipitation of a Ca-phosphate solid that incorporates U; (c) precipitation of Ca-phosphate mineral (apatite group minerals) that coats existing uranium phases (i.e., U in calcite, U in Fe-oxides), reducing uranium leaching; and (d) aqueous Ca-U-carbonate species adsorption onto apatite. Given the significant amount of apatite precipitation, other U phases such as carbonates could also coprecipitate with apatite. To quantify differences in solubility, leachability, and phases of uranium between pre- and post-PO 4 -treated sediments, different types of analyses were conducted, including analysis of uranium in (a) a carbonate solution extraction from sediment over 1000 h (41.67 days), (b) six sequential liquid extractions from sediment over approximately 1 week, (c) leaching of uranium from sediments in one dimensional (1-D) column experiments over 2 months, and (d) solid phase characterization of select sediments. An additional extraction and solid phase measurements were conducted to evaluate phosphate precipitate formation. Metals were also analyzed in sequential liquid extractions as indicators of (a) amendment injection delivery, (b) co-contaminant movement, and (c) changes in solid phases. Aqueous and solid phase carbonate measurements were also conducted to evaluate changes in carbonates.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Literature Review of Documented Persistent Secondary Uranium Sources at DOE LM Sites

The U.S. Department of Energy Office of Legacy Management (LM) has the responsibility to protect human health and the environment at 101 legacy uranium sites across the nation by implementing long-term surveillance and maintenance requirements. Included in these responsibilities is to provide for the safe and environmentally sound disposal, long-term stabilization, and control of uranium mill tailings in a manner that minimizes or eliminates radiation health hazards to the public at 21 Uranium Mill Tailings Radiation Control Act (UMTRCA) Title I sites; 6 UMTRCA Title II sites; and 9 Comprehensive Environmental Response, Compensation, and Liability Act/Resource Conservation and Recovery Act sites. These sites are former uranium mills (processing sites), or sites with wastes from processing sites encapsulated in engineered disposal cells (disposal sites), or sites where components of atomic weapons were manufactured. During site characterization, groundwater contamination was often discovered and evaluated or modeled for future movement with the inclusion of uranium sorption in the groundwater plume. Much of this original work did identify uranium processing wastes as the original contaminant source. However, more recent work has identified the existence and influence of persistent secondary uranium sources that may prevent uranium in groundwater from attenuating as quickly as initial evaluations or modeling indicated. By understanding these processes, better decisions can be made to choose the appropriate remediation and closure strategies, identify long-term surveillance and maintenance activities, and more accurately estimate life-cycle costs. The purpose of this report is to summarize the literature available on documented persistence secondary uranium sources at LM sites as part of the Applied Studies and Technology Persistent Secondary Contaminant Sources Project.

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Subcritical Californium Source Drive Noise Analysis Measurements With Unreflected Uranium (93.15) Hydride

On July 6, 1989, subcritical californium source-driven noise analysis (CSDNA) measurements were performed with bare uranium hydride cylindrical assemblies at the Los Alamos National Laboratory Critical Experiments Facility in KIVA 1. Three configurations of ~7.5 cm radius-enriched (93.15 wt. % 235 U) uranium hydride with a density of ~10 g/cm 3 cylinders were assembled with uranium hydride heights of ~11, ~14, and ~16 cm. The uranium hydride (~2 and ~3 cm high) was in thin-welded stainless steel cans. The neutron multiplication factors obtained on-line from the measured ratios of spectral densities were 0.942 ± 0.002, 0.917 ± 0.003, and 0.867 ± 0.004 for uranium hydride heights of ~16, ~14, and ~11 cm., respectively. Neutron multiplication factors for these three configurations calculated by Los Alamos National Laboratory Monte Carlo methods were 0.952 ± 0.005, 0.922 ± 0.005, and 0.860 ± 0.005, all of which are in good agreement with the measurements. The break frequency noise analysis data could be fitted to obtain the prompt neutron decay constant at all subcritical states. Some data presented in this report are from notes that are not in the logbooks. A discussion of the two different point kinetics theories of the measurements that illustrated the deficiencies of the rigorous theory at low neutron multiplication factors (k eff < 0.80) is given in an Appendix. These measurements may be the only configuration of unreflected, highly enriched uranium hydride configuration assembled. The presence of hydrogen diluted the uranium density, decreasing the reactivity, but this is offset by slowing down the neutron energy to the energy ranges of higher-fission cross sections. Extrapolations to delayed critical indicate that adding one more 3 cm can and one more 2 cm can would result in the unreflected cylindrical system being slightly above critical with a critical mass of ~37 kg, which is considerably less than the critical mass of an unreflected and unmoderated highly enriched uranium metal sphere. An unreflected, highly enriched uranium hydride sphere would have a critical mass less than 37 kg.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Benchmark Gap Assessment for the Manufacturing of High-Assay Low-Enriched Uranium Fuels

This document develops basic critical conditions for spheres—moderated and unmoderated, as well as reflected and unreflected—in consideration of nuclear criticality safety of a potential fuel production facility producing high-assay low-enriched uranium (HALEU) fuel of several different types like tristructural-isotropic (TRISO), uranium metal and alloys, oxide and non-metallic forms. In addition to spherical arrangements, TRISO particle manufacturing process–specific equipment is modeled as it would be for the criticality safety analysis. The objective is to develop representative systems that can then be used for comparison with existing benchmarks. SCALE/TSUNAMI is used to assess the similarity index between these systems to assess validation gaps for possible fuel production applications of proposed advanced reactors. Several different fuel types were evaluated, including TRISO, uranium metal, uranium molybdenum, uranium zirconium, uranium dioxide, uranium nitride, uranium hydride, U-ZrH, and uranium chloride. This selection of fuel types covers a breadth of proposed reactor types, as well as intermediate steps in the production and fabrication of the fuel

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

{sup 232,234,236}U Removal from Contaminated Waste Uranium Hexafluoride in a Double Cascade

Two schemes with double cascades are presented for purifying waste uranium hexafluoride with high {sup 232,234,236}U content. A large flow of native uranium hexafluoride and a low flow of waste uranium hexafluoride are fed into the first cascade. One of the external outgoing streams contains low-enrichment uranium hexafluoride with prescribed {sup 235}U concentration <5%. The {sup 235}U concentration of the second outgoing stream coincides with the feed concentration of waste uranium hexafluoride. {sup 232,234,236}U concentration reduction occurs in this stream, corresponding to purified waste uranium hexafluoride. The obtained products can be used effectively for enrichment in a cascade meeting ASTM C 996–15 specifications for low-enrichment commercial uranium.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

New approach to gamma scans for processed natural uranium at a FUSRAP site - 15470

The Superior Steel Site is part of the FUSRAP because the former facility processed natural uranium metal in support of the Atomic Energy Commission (AEC) fuel-element development program in the 1950's. Previous investigations of the site have identified uranium contamination both inside and outside of the building associated with the uranium work and some limited remediation was performed in the past. As part of the remedial investigation (RI) process for the site, gamma scan surveys were completed in order to define the nature and extent of elevated residual uranium associated with AEC activities. One of the challenges with investigating for processed natural uranium versus unprocessed natural uranium is that the processed uranium is practically devoid of its decay progeny, which produce gamma photon radiation emissions commonly relied upon to detect the presence of uranium. To address this challenge, a sodium iodide (NaI) detector was designed and fabricated to optimize the signal to noise ratio for U-238 low energy gammas (59-127 keV) and to reduce interferences from other radionuclides that may be present from non-FUSRAP sources. Gamma scan surveys were performed with the optimized NaI detector in conjunction with typical, commercially available 0.35 liter NaI detectors. The results of this survey and a comparison between the detectors is presented. (authors)

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Assessment of a Hydroxyapatite Permeable Reactive Barrier to Remediate Uranium at the Old Rifle Site, Colorado - 16193

We have performed an initial evaluation and testing program to assess the effectiveness of a hydroxyapatite (Ca{sub 10}(PO{sub 4}){sub 6}(OH){sub 2}) permeable reactive barrier and source area treatment to decrease uranium mobility at the Department of Energy (DOE) former Old Rifle uranium mill processing site in Rifle, western Colorado. Uranium ore was processed at the site from the 1940's to the 1970's. The mill facilities at the site as well as the uranium mill tailings previously stored there have all been removed. Groundwater in the alluvial aquifer beneath the site still contains elevated concentrations of uranium and is currently used for field tests to study uranium behavior in groundwater and investigate potential uranium remediation technologies. The technology investigated in this work is based on in situ formation of apatite in sediment to create a subsurface apatite PRB and also for source area treatment. The process is based on injecting a solution containing calcium citrate and sodium into the subsurface for constructing the PRB within the uranium plume. As the indigenous sediment micro-organisms biodegrade the injected citrate, the calcium is released and reacts with the phosphate to form hydroxyapatite (precipitate). This paper reports on proof-of-principle column tests with Old Rifle sediment and synthetic groundwater. (authors)

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Heat Transfer in a Molten Natural Uranium Nuclear Reactor With Thermal Storage

Previous papers describe a method for controlling a thermal nuclear reactor by moderator displacement between the reactor core and the reflector. The low neutron loss and high control range of this method enable a design for a molten natural uranium fueled and cooled heavy water moderated reactor. The design is geometrically similar to CANDU (Canadian Deuterium Uranium) reactors but with fewer, larger, vertically oriented fuel tubes. The large fuel tubes have a mixed spectrum which is largely thermal at the periphery of the tubes with a very hard spectrum in the large central region of the tube. This configuration provides a fast fission rate of around 15% (mostly of U-238) and an initial conversion ratio of around 1.15. It is a hypothetical reactor because it is unclear what materials could actually be used to fabricate the fuel tubes and other primary coolant plumbing. The molten uranium serves both as the fuel and the primary coolant and as such is continuously circulated through the fuel tubes in the reactor core, the primary heat exchange, and back to the the reactor core. This means that at any point in time all the fuel has the same isotopic configuration no matter where it is in the reactor or heat exchanger. Over time the isotopic configuration changes, but it changes uniformly for all the fuel. Uranium melts at 1135 deg. C, so a proposed temperature range for the circulating molten uranium is 1200 deg. C at the exit of the heat exchanger and entry to the core fuel tubes and 1400 deg. C at the exit from the core fuel tubes and the entry into the heat exchanger. The advantages of this design include: 1. Reduced nuclear proliferation concern because of natural uranium fuel. 2. High conversion ratio and large fuel mass provides 30 to 100 year fuel life. 3. No heavy metal waste because fissile content increases over the fuel life. 4. High output temperatures are suitable for high efficiency turbine generators. This paper discusses the heat transfer in the molten natural uranium fueled reactor described above and in the cited paper in the simple case and when the reactor is combined with a thermal storage unit which is composed of ordinary salt (NaCl). The proposed molten uranium fueled and cooled nuclear reactor works particularly well when coupled with a molten salt heat storage unit, a process heat user, and high Efficiency air-Brayton cycle turbine generators which can also add energy to the hot air output of the tin/air heat exchanges by burning some natural gas or hydrogen. The combination can provide highly variable electrical output to the grid to accommodate large daily and seasonal mismatches between electrical demand and supply from variable sources such as wind and solar. Future work includes modeling of the temperatures throughout the molten salt heat storage unit under varying charge and discharge cycles.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗

Physics and Environmental Assessments for a Heavy-Water Moderated, Molten Uranium Reactor Concept

Previous papers describe a method for controlling a thermal nuclear reactor by moderator displacement between the reactor core and the reflector. The low neutron loss and high control range of this method enable a design for a molten natural uranium fueled and cooled heavy water moderated reactor. The design is geometrically similar to CANDU (Canadian Deuterium Uranium) reactors but with fewer, larger, vertically oriented fuel tubes. The fuel tubes contain molten natural uranium as both the fuel and the coolant instead of fuel rods and water coolant. The large fuel tubes have a mixed spectrum which is largely thermal at the periphery of the tubes with a very hard spectrum in the large central region of the tube. This configuration provides a fast fission rate of around 15% (mostly of U-238) and an initial conversion ratio of around 1.15. It is a hypothetical reactor because it is unclear what materials could actually be used to fabricate the fuel tubes and other primary coolant plumbing. The molten uranium serves both as the fuel and the primary coolant and as such is continuously circulated through the fuel tubes in the reactor core, the primary heat exchange, and back to the the reactor core. This means that at any point in time all the fuel has the same isotopic configuration no matter where it is in the reactor or heat exchanger. Over time the isotopic configuration changes, but it changes uniformly for all the fuel. Uranium melts at 1135 deg. C, so a proposed temperature range for the circulating molten uranium is 1200 deg. C at the exit of the heat exchanger and entry to the core fuel tubes and 1400 deg. C at the exit from the core fuel tubes and the entry into the heat exchanger. The advantages of this design include: 1. Reduced nuclear proliferation concern because of natural uranium fuel. 2. High conversion ratio and large fuel mass provides 30 to 100 year fuel life. 3. No heavy metal waste because fissile content increases over the fuel life. 4. High output temperatures are suitable for high efficiency turbine generators. This assessment will examine three perspectives: reactor physics, regional grid management, and global resource utilization and impact. This assessment will examine three perspectives: reactor physics, regional grid management, and global resource utilization and impact. The proposed reactor type can generate much of the future CO{sub 2} emission free electric power demand with a low impact on total uranium required to be mined, zero heavy metal waste produced, zero enrichment capability required, and capacity (with thermal storage) to meet fluctuating demand. There are engineering issues to be addressed before such a reactor can be built, but thanks to the demand for high efficiency gas turbines and other high temperature applications, high temperature materials and technology are developing rapidly. An operating temperature of 1400 degrees C does not seem unreasonable in the near future. The implied advantages of this reactor type compared to other existing or proposed reactors suggest that further work on the issues raised would be well worthwhile. (authors)

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗

Effect of Minerals on the Removal of Uranium (VI) in the Presence of Humic Acid and Colloidal Silica - 19406

Uranium is one of the key contaminants of concern in groundwater as a result of past nuclear processing activities at the Department of Energy (DOE) facilities such as the Savannah River Site (SRS) in Aiken, South Carolina. SRS was one of the major nuclear processing facilities during the Cold War where plutonium was produced. Beginning with the implementation of the environmental cleanup program in 1981, SRS has become a hazardous waste management facility responsible for the storage and remediation of contaminated soil and groundwater from radionuclides. Approximately 1.8 billion gallons of acidic waste containing radionuclides and dissolved heavy metals was disposed in the F/H Area seepage basins. This led to the unintentional creation of highly contaminated groundwater plumes, consisting of radionuclides with an acidic pH between 3 and 5.5. The acidity of the plumes contributed to the mobility of several constituents of concern (COC) such as tritium ({sup 3}H), uranium-238 ({sup 238}U), iodine-129 ({sup 129}I), and strontium-90 ({sup 90}Sr) for the F-Area plume and {sup 3}H, {sup 90}Sr and mercury for the H-Area plume. This investigation will focus on uranium in the oxidation state +6 (U(VI)), which is a key contaminant of concern in the groundwater plume of the FArea. Initially, the pump-treat-reinject system was implemented from 1997 to 2003 to remove contaminants from polluted groundwater. Downgrade groundwater within the system would be pumped to the water treatment facility and re-injected upgrade within the aquifer. The effectiveness and sustainability of this process diminished over time. Therefore, it was discontinued and replaced with a funnel-and-gate process in 2004. This new process injects sodium hydroxide directly into the gates of the F-Area groundwater to effectively raise pH levels. By raising the pH of the groundwater, a treatment zone is created by reversing the acidic nature of the contaminated sediments and producing a negative net charge on the surface of sediment particles. As a result, the adsorption of cationic contaminants is expected to be enhanced. So far, this process has resulted in a decrease of {sup 90}Sr and {sup 238}U concentrations, though the concentration of iodine has been unaffected by this treatment. The solution used for the injections contains a high carbonate alkalinity in order to overcome the surface acidic conditions and natural partitions in the groundwater system. To maintain the neutral pH in the treatment zone, systematic injections are required. The continuous use of high concentrations of a carbonate solution to raise pH could re-mobilize uranium previously adsorbed within the treatment zone, though this has not been observed in the monitoring data. Humic substances (HS) are major components of soil organic matter. HS are polyfunctional organic macromolecules formed by the chemo-microbiological decomposition of biomass or dead organic matter. These substances are usually divided into three main fractions: humin (insoluble at all pH values), humic acid (soluble at pH greater than 3.5), and fulvic acid (soluble at all pH values). Humic acid carries a large number of functional groups such as aromatic rings, carboxyl groups, phenols, aliphatic chains, etc. Humic acid is an important ion exchange and metal complexing ligand with a high complexation capacity. The ability of humic acid to chemically bind to metals influences in their migration behavior and fate in natural systems. Various studies have suggested that the retention of U(VI) via sorption in the presence of humic acid is a complex process. For instance, humic acid can form an organic coating at the surface of minerals, which can enhance the sequestration of metals. Ivanov et al. (2012) studied the sorption of U(VI) sorption onto bentonite in the presence and absence of humic acid. The study found that uranium sorption in the presence of humic acid was enhanced at low pH (below 3.8) while at moderate pH (3.8 and 6.5) uranium sorption was reduced compared to the absence of humic acid. At high pH (7 and 9), uranium sorption was reduced for both the presence and absence of humic acid. Also, Krepelova et al. (2007) not only found that U(VI) sorption onto kaolinite was influenced by pH, U(VI) concentration, the presence of inorganic carbon species, and humic acid but also that U(VI) preferred to be adsorbed onto kaolinite as a uranyl-humate complex. This investigation analyzed the mechanisms of the synergetic interactions of humic acid and colloidal silica on the removal of uranium in the presence of pure minerals such as quartz, kaolinite and goethite which are characteristic of the F/H area. (authors)

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Reveal of Uranium Bioremediation Mechanisms by Bacillus Species through Proteomics Studies

Radionuclides, such as Uranium (U) and heavy metals continue to pose threats to the ecosystem health and processes at the Department of Energy (DOE) managed, Savannah River Site (SRS), located along the Savannah River near Aiken, SC. Such co-contaminated environments are difficult to remediate using conventional excavation and disposal or pump-and-treat approaches. Globally, more than 109 tons of uranium contaminated areas pose a long term threat to human and ecological health. Even with presented low concentrations in the brain, central nervous effects are still observed. Uranium and depleted uranium (DU) have long term effects on the kidneys. Some small general health effects include severe headaches and breathing problems. Uranus ions are toxic to living cells because they inhibit metabolism of carbohydrates by blocking ATP binding sites. Bioremediation by microorganisms represents an alternative solution, which is advantageous because of the possibility of biosorbent regeneration, cost-effectiveness, increased metal removal and easy recovery of some valuable metals. Bacillus sp. bacterium was previously used in the bioremediation of heavy metals in coal mine run off waters of SRS. However, its ability to bioremediate uranium was unknown so far. Hence, in the present study, uranium bioremediation by Bacillus sp. bacterium was investigated. The mechanism of bioremediation was also revealed through proteomics studies. Heavy metals contamination poses a serious threat to water, soil and human health. Soil and water are contaminated due to excessive exploitation of uranium mines for generation of nuclear energy and weaponry. It is not degradable easily and persist in soil and water for a long period of time due to its long half- life. Savannah river site (SRS) is one of the uranium contaminated sites. The physical or chemical remediation techniques are costly and complex. Microbial system approaches with competent bacteria has received increased attention due to its adaptability in various environmental matrices and cost effectiveness. However, even though there are multiple suggested pathways (F1), the specific mechanisms that drive this behavior are still unclear, especially with popular microorganisms such as Bacillus species. In a previous research (Ibeanusi et al, 2003) Bacillus sp. was shown to detoxify and precipitate a variety of heavy metals in coal pile runoff waters of SRS site. Additionally, genomic analysis demonstrated that this microorganism posses multiple attributes for chemical transport regulation and metabolic pathways. U remediation occurs during the first 20 hours of exposure. During this time period, Bacillus sp. may work primarily under two mechanisms - sorption and accumulation. These two mechanisms simultaneously work to protect the microorganism from high concentrations. Figure 10 demonstrates that certain proteins are up regulated and down regulated under extreme stressful conditions. Membrane fraction proteins were up regulated. Cytosolic fraction proteins were down regulated. This protein information coincides with the adsorption behavior. Bacillus sp. is a good candidate for U remediation at various concentrations.

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Study of an Unrefined Humate Solution as a Possible Attenuation-based Remedy for Uranium Contamination in Acidic Groundwater - 20351

The Savannah River Site (SRS), joined the environmental cleanup program in 1981 after the Cold War, and was designated as a hazardous waste management facility. About 1.8 billion gallons of acid wastes were disposed into the F/H Area Seepage Basin that included many radionuclides and dissolved metals, resulting in highly contaminated groundwater plumes with pH of 3 - 5.5. The acidity of the plumes contributes to the mobility of several constituents of concern (COC) such as H-3, U-238, I-129, and Sr-90 for the F-Area plume and H-3, Sr-90 and mercury for the H-Area plume. An active treatment (pump-and-treat and re-injection) system was constructed and put in place in 1997 to address the removal of metals and radionuclides from the contaminated groundwater. As remediation projects advanced, active treatments were transitioned to more passive or enhanced-passive approaches such as the subsurface barrier with base injection system, which has been controlling the mobility of contaminants. However, new and more efficient attenuation-based remedies are always sought. Several studies have proposed that humic substances can be used to remediate sites contaminated with heavy metals by creating a permeable reactive barrier. Humic substances (HS) are major components of soil organic matter. HS are polyfunctional organic macromolecules formed by the chemo-microbiological decomposition of biomass or dead organic matter. These substances are usually divided into three main fractions: humin (insoluble at all pH values), humic acid (soluble at pH greater than 3.5), and fulvic acid (soluble at all pH values). Humic substances are major components of the soil at SRS and, in addition, are also helpful in the removal process of uranium. This research focuses on uranium (VI), which is a key contaminant of concern in the F-Area groundwater plume. The interaction of uranium with sediment in the presence or absence of humic substances involves complex mechanisms that are not yet well understood. The interaction of U(VI) with humic substances can affect the adsorption of U on sediment, altering its mobility in the subsurface. The objective of this study is to study the mobility of uranium in the presence of humic acid and to determine if sediments amended by humic acid can enhance the sorption of heavy metals onto sediments. In this research, experiments were conducted using background (clean) F-Area aquifer sediments to understand and predict uranium mobility. A blended material, humate, containing both humic and fulvic acids and a chemically modified humate (KW15 modified humic or mod-HA) was studied as a possible amendment for uranium remediation in SRS groundwater. Batch experiments were conducted in triplicates using 20 ml of aqueous suspension in DI water containing SRS sediment and mod-HA and studied the effect of pH, kinetics of humate sorption onto SRS sediment and also studied the sorption of uranium onto mod-HA amended SRS sediment. Results indicate that mod-HA amended sediment increases uranium removal significantly. (authors)

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