Alpha and gamma radiation effects on air-water systems at high gas/liquid ratios

Radiolysis tests were conducted on air-water systems to examine the effects of radiation on liquid phase chemistry under high gas/liquid volume (G/L) ratios that are characteristic of an unsaturated nuclear waste repository setting. Test parameters included temperatures of 25, 90, and 200{degrees}C; gamma vs. alpha radiation; dose rates of {approximately}3500 and 50,000 rad/h; and G/L ratios of 10 and 100. Formate, oxalate, and total organic carbon contents increased during irradiation of the air-water systems in gamma and alpha tests at low-dose rate ({approximately}3500 rad/h). Increases in organic components were not observed for tests run at 200{degrees}C or high-dose rates (50,000 rad/h). In the tests where increases in organics occurred, the formate and oxalate were preferentially enriched in solutions that were rinsed from the test vessel walls. Nitrate (NO{sub 3}{sup {minus}}) is the dominant anion produced during the radiolysis reactions. Significant nitrite (NO{sub 2}{sup {minus}}) also occurs in some high-dose rate tests, with the reduced form of nitrogen possibly resulting from reactions with the test vessels. These results indicate that nitrogen acids are being produced and concentrated in the limited quantities of solution present in the tests. Nitrate + nitrite production varied inversely with temperature, with the lowest quantities being detected for the higher temperature tests. The G(NO{sub 3}{sup {minus}} + NO{sub 2}{sup {minus}}) values for the 25, 90, and 200{degrees}C experiments with gamma radiation are 3.2 {+-} 0.7, 1.3 {+-} 1.0, and 0.4 {+-} 0.3, respectively. Thus, the elevated temperatures expected early in the life of a repository may counteract pH decreases resulting from nitrogen acid production. Little variation was observed in G values as a function of dose rate or gas/liquid ratio

Grain boundary corrosion and alteration phase formation during the oxidative dissolution of UO{sub 2} pellets

Alteration behavior of UO{sub 2} pellets following reaction under unsaturated drip-test conditions at 90 C for up to 10 years was examined by solid phase and leachate analyses. Sample reactions were characterized by preferential dissolution of grain boundaries between the original press-sintered UO{sub 2} granules comprising the samples, development of a polygonal network of open channels along the intergrain boundaries, and spallation of surface granules that had undergone severe grain boundary corrosion. The development of a dense mat of alteration phases after 2 years of reaction trapped loose granules, resulting in reduced rates of particulate U release. The paragenetic sequence of alteration phases that formed on the present samples was similar to that observed in surficial weathering zones of natural uraninite (UO{sub 2}) deposits, with alkali and alkaline earth uranyl silicates representing the long-term solubility-limiting phases for U in both systems

Apatite- and Monazite-Bearing Glass-Crystal Composites for the Immobilization of Low-level Nuclear and Hazardous Wastes

This study demonstrates that glass-crystal composite waste forms can be produced from waste streams containing high proportions of phosphorus, transition metals, and/or halides. The crystalline phases produced in crucible-scale melts include apatite, monazite, spinels, and a Zr-Si-Fe-Ti phase. These phases readily incorporated radionuclide and toxic metals into their crystal structures, while corrosion tests have demonstrated that glass-crystal composites can be up to 300-fold more durable than simulated high-level nuclear waste glasses, such as SRL 202U

An Evaluation of Glass-Crystal Composites For the Disposal of Nuclear and Hazardous Waste Materials

Waste forms made of a glass-crystal composite (GCC) are being evaluated at Argonne National Laboratory for their potential use in the disposal of low-level nuclear and hazardous waste materials. This waste form is being developed within the framework strategy of DOE`s minimum Additive Waste Stabilization (MAWS) Program. The MAWS protocol involves the blending of multiple waste streams to achieve an optimal feed composition, which eliminates the need to use large amounts of additives to produce an acceptable waste form. The GCCs have a particularly useful utility in their ability to incorporate waste streams with high metal contents, including those that contain large amounts of scrap metals, and in their potential for sequestering radionuclide and hazardous constituents in corrosion-resistant mineral phases. This paper reports the results from tests conducted with simulated feeds representative of potential DOE and industry waste streams. Topics addressed include the partitioning of various radioactive and hazardous constituents between the glass and crystalline portions of the waste form, the development of secondary phases on the altered sample surfaces during corrosion testing, and the fate of waste components during corrosion testing, as indicated by elements released to solution and microanalysis of the reacted solid samples

Effects of radionuclide decay on waste glass behavior: A critical review

This paper is an extension of a chapter in an earlier report [1] that provides an updated review on the status of radiation damage problems in nuclear waste glasses. This report will focus on radiation effects on vitrified borosilicate nuclear waste glasses under conditions expected in the proposed Yucca mountain repository. Radiation effects on high-level waste glasses and their surrounding repository environment are important considerations for radionuclide immobilization because of the potential to alter the glass stability and thereby influence the radionuclide retentive properties of this waste form. The influence of radionuclide decay on vitrified nuclear waste may be manifested by several changes, including volume, stored energy, structure, microstructure, mechanical properties, and phase separation. Radiation may also affect the composition of aqueous fluids and atmospheric gases in relatively close proximity to the waste form. What is important to the radionuclide retentive properties of the repository is how these radiation effects collectively or individually influence the durability and radionuclide release from the glass in the event of liquid water contact

Evaluation of standard durability tests towards the qualification process for the glass-zeolite ceramic waste form

Glass-bonded zeolite is being developed as a potential ceramic waste form for the disposition of radionuclides associated with the Department of Energy`s (DOE`s) spent nuclear fuel conditioning activities. The utility of several standard durability tests was evaluated as a first step in developing methods and criteria that can be applied towards the process of qualifying this material for acceptance into the DOE Civilian Radioactive Waste Management System. The effects of pH, leachant composition, and sample surface-area-to leachant-volume ratios on the durability test results are discussed, in an attempt to investigate the release mechanisms and other physical and chemical parameters that are important for the acceptance criteria, including the establishment of appropriate test methodologies required for product consistency measurements

Effects of alpha and gamma radiation on glass reaction in an unsaturated environment

Radiation may effect the long-term performance of glass in an unsaturated repository site by interacting with air, water vapor, or liquid water. The present study examines (1) the effects of alpha or gamma irradiation in a water vapor environment, and (2) the influence of radiolytic products on glass reaction. Results indicate that nitric and organic acids form in an irradiated water vapor environment and are dissolved in thin films of condensed water. Glass samples exposed to these conditions react faster and have a different assemblage of secondary phases than glasses exposed to nonirradiated water vapor environments. 23 refs., 4 figs., 2 tabs

Development of test acceptance standards for qualification of the glass-bonded zeolite waste form. Interim annual report, October 1995--September 1996

Glass-bonded zeolite is being developed at Argonne National Laboratory in the Electrometallurgical Treatment Program as a potential ceramic waste form for the disposition of radionuclides associated with the US Department of Energy`s (DOE`s) spent nuclear fuel conditioning activities. The utility of standard durability tests [e.g. Materials Characterization Center Test No. 1 (MCC-1), Product Consistency Test (PCT), and Vapor Hydration Test (VHT)] are being evaluated as an initial step in developing test methods that can be used in the process of qualifying this material for acceptance into the Civilian Radioactive Waste Management System. A broad range of potential repository conditions are being evaluated to determine the bounding parameters appropriate for the corrosion testing of the ceramic waste form, and its behavior under accelerated testing conditions. In this report we provide specific characterization information and discuss how the durability test results are affected by changes in pH, leachant composition, and sample surface area to leachant volume ratios. We investigate the release mechanisms and other physical and chemical parameters that are important for establishing acceptance parameters, including the development of appropriate test methodologies required to measure product consistency

Repository relevant testing applied to the Yucca Mountain Project

The tuff beds of Yucca Mountain, Nevada, are currently being investigated as a site for the disposal of high-level nuclear waste in an underground repository. If this site is found suitable, the repository would be located in the unsaturated zone above the water table, and a description of the site and the methodology of assessing the performance of the repository are described in the Site Characterization Plan (SCP). While many factors are accounted for during performance assessment, an important input parameter is the degradation behavior of the waste forms, which may be either spent fuel or reprocessed waste contained in a borosilicate glass matrix. To develop the necessary waste form degradation input, the waste package environment needs to be identified. This environment will change as the waste decays and also is a function of the repository design which has not yet been finalized. At the present time, an exact description of the waste package environment is not available. The SCP does provide an initial description of conditions that can be used to guide waste form evaluation. However, considerable uncertainty exists concerning the conditions under which waste form degradation and radionuclide release may occur after the waste package containment barriers are finally breached. The release conditions that are considered to be plausible include (1) a {open_quotes}bathtub{close_quotes} condition in which the waste becomes fully or partially submerged in water that enters the breached container and accumulates to fill the container up to the level of the breach opening, (2) a {open_quotes}wet drip{close_quotes} or {open_quotes}trickle through{close_quotes} condition in which the waste form is exposed to dripping water that enters through the top and exits the bottom of a container with multiple holes, and (3) a {open_quotes}dry{close_quotes} condition in which the waste form is exposed to a humid air environment

Microscopic characterization of crystalline phases in waste forms

Transmission electron microscopy (TEM) has been used to determine the microstructure of crystalline phases present in zirconium- and titanium-bearing glass crystalline composite (GCC) waste forms. The GCC materials were found to contain spinels (maghemite), zirconolites, perovskites (CaTiO{sub 3}) and plagiociase feldspar (anorthite) mineral phases. The structure of the uranium and cerium-bearing monoclinic zirconolite was characterized by medium resolution TEM imaging and electron and X-ray diffraction (XRD). The phase was found to contain high levels of iron in comparison to Synroc-type zirconolites. Excess zirconium in zirconolite has resulted in martensitic baddeleyite (ZrO{sub 2}) formation. Anorthite (CaAl{sub 2}Si{sub 2}O{sub 8}) was present as elongated crystallites within a calcium-rich aluminosilicate glass. Lead and iron-bearing anorthite lying along distinct precipitates were occasionally observed within the an crystallographic planes