Thomas J. Gerding

Uranium release and secondary phase formation during unsaturated testing of UO2 at 90°C

Abstract Experimental results indicate that UO2 will readily react after being exposed to dripping oxygenated ground water at 90°C. A pulse of rapid U release, combined with the formation of dehydrated schoepite characterizes reactions between one to two years. Rapid dissolution of intergrain boundaries and spallation of UO2 granules appears to be responsible for the rapid U release. Less than 5% of the U is released in a soluble or suspended form. After two years, U release rates decline and a more stable assemblage of uranyl silicate phases form by incorporating cations from the leachant. Uranophane, boltwoodite, and sklodowskite are the final solubility-limiting phases for U in these tests. This observed paragenetic sequence (from uraninite to schoepite to uranyl silicates) is identical to those observed in weathered uraninite deposits. Dispersion of particulate matter may be an important release mechanism for U and other radionuclides in spent nuclear fuel.

Experimental Hydration Studies of Natural and Synthetic Glasses

The results of a series of hydration experiments on natural glasses (Hawaiian basalt, obsidian) and the nuclear waste glass WV-44 done to examine laboratory methods of accelerating reaction processes are summarized. The glasses were reacted in hydrothermal solution and in saturated vapor water. It was found that different reaction rates and processes were found using the differing conditions, and that laboratory efforts to accelerate and duplicate natural processes must account for the physical processes that occur naturally.

Parametric Effects on Glass Reaction in the Unsaturated Test Method

The Unsaturated Test Method has been applied to study glass reaction under conditions that may be present at the potential Yucca Mountain site, currently under evaluation for storage of reprocessed high-level nuclear waste. The results from five separate sets of parametric experiments are presented wherein test parameters ranging from water contact volume to sensitization of metal in contact with the glass were examined. The most significant effect was observed when the volume of water, as controlled by the water inject volume and interval period, was such to allow exfoliation of reacted glass to occur. The extent of reaction was also influenced to a lesser extent by the degree of sensitization of the 304L stainless steel. For each experiment, the release of cations from the glass and alteration of the glass were examined. The major alteration product is a smectite clay that forms both from precipitation from solution and from in-situ alteration of the glass itself. It is this clay that undergoes exfoliation as water drips from the glass. A comparison is made between the results of the parametric experiments with those of static leach tests. In the static tests the rates of release become progressively reduced through 39 weeks while, in contrast, they remain relatively constant in the parametric experiments for at least 300 weeks. This differing behavior may be attributable to the dripping water environment where fresh water is periodically added and where evaporation can occur.

Reaction of glass during gamma irradiation in a saturated tuff environment. Part 1. SRL 165 glass

The influence of gamma irradiation on the reaction of actinide-doped borosilicate glass (SRL 165) in a saturated tuff environment has been studied in a series of tests lasting up to 56 days. The following conclusions were reached. The reaction of, and subsequent actinide release from, the glass depends on the dynamic interaction between radiolysis effects, which cause the solution pH to become more acidic; glass reaction, which drives the pH more basic; and test component interactions that may extract glass components from solution. The use of large gamma irradiation dose rates to accelerate reactions that may occur in an actual repository radiation field may affect this dynamic balance by unduly influencing the mechanism of the glass-water reaction. Comparisons between the present results and data obtained by reacting similar glasses using MCC-1 and NNWSI rock cup procedures indicate that the irradiation conditions used in the present experiments do not dramatically influence the reaction rate of the glass. 8 figs., 9 tabs.

NNWSI Phase II materials interaction test procedure and preliminary results

The Nevada Nuclear Waste Storage Investigations (NNWSI) project is investigating the volcanic tuff beds of Yucca Mountain, Nevada, as a potential location for a high-level radioactive waste repository. This report describes a test method (Phase II) that has been developed to measure the release of radionuclides from the waste package under simulated repository conditions, and provides information on materials interactions that may occur in the repository. The results of 13 weeks of testing using the method are presented, and an analog test is described that investigates the relationship between the test method and expected repository conditions. 9 references, 10 figures, 11 tables.

The reaction of glass during gamma irradiation in a saturated tuff environment: Part 3, long-term experiments at 1 x 10{sup 4}rad/hour

Savannah River Laboratory 165 type glass was leached with equilibrated J-13 groundwater at 90{degree}C for times up to 182 days. These experiments were performed as part of an effort by the Nevada Nuclear Waste Storage Investigations Project to assess the importance of radiation effects on repository performance and waste glass corrosion. The gamma radiation field used in this work was 1. 0 +- 0.2 x 10{sup 4} rad/h. Glass dissolution is notably incongruent throughout the entire experimental periods and normalized releases follow the sequence Li {ge} Na {ge} B {approx_equal} U {ge} Si. The normalized leach rates of these elements, as well as the measured growth rates of the reaction layers, decreased with time. The only significant variation observed in the abundance of anions is the systematic decrease in NO{sub 3}/sup {minus}//NO{sub 2}/sup {minus}/ ratio from the starting EJ-13 groundwater to the EJ-13 blank experiments to the tuff- and glass-containing experiments. A leaching model that is consistent with the observed solution data and depth profiles is presented. The applicability and limitation of the present results in predicting the actual interactions that may occur in the NNWSI repository are discussed. 35 refs., 30 figs., 12 tabs.

The performance of actinide-containing SRL 165 type glass in unsaturated conditions

As part of the effort by the Nevada Nuclear Waste Storage Investigations (NNWSI) Project to evaluate the volcanic tuff beds of Yucca Mountain, Nevada, as a repository for the permanent storage of high-level nuclear waste, the interaction of actinide-doped Savannah River Laboratory (SRL) 165 type glass with the unsaturated repository environment has been studied. The NNWSI Unsaturated Test method has been used, and the results from batch and continuous tests completed through 18 months demonstrate that several interactions are important for controlling both the reaction of the glass and the release of radionuclides. These interactions include (1) the reaction between the glass and moist air with interludes of liquid water contact, which results in the release of alkali metals from the glass; and (2) the reaction between standing water, glass, and presensitized 304 L type stainless steel which results in breakdown of the glass matrix and the release of radionuclides from the glass-metal assemblage. A comparison of the results of the Unsaturated Test with those of parametric experiments illustrates the importance of presensitized steel in enhancing the glass reaction, and demonstrates the applicability of the Unsaturated Test to those conditions anticipated to exist in the NNWSI repository horizon. 10 refs., 8 figs., 1 tab.

Application of the NNWSI [Nevada Nuclear Waste Storage Investigations] Unsaturated Test Method to Actinide Doped SRL [Savannah River Laboratory] 165 Type Glass

The results of tests done using the Unsaturated Test Method are presented. These tests, done to determine the suitability of glass in a potential high-level waste repository as developed by the Nevada Nuclear Waste Storage Investigations Project, simulate conditions anticipated for the post-containment phase of the repository when only limited contact between the waste form and water is expected. The reaction of glass occurs via processes that are initiated due to glass/water vapor and glass/liquid water contact. Vapor interaction results in the initiation of an exchange process between water and the more mobile species (alkalis and boron) in the glass. The liquid reaction produces interactions similar to those seen in standard leaching tests, except due to the limited amount of water present and the presence of partially sensitized 304L stainless steel, the formation of reaction products greatly exceeds that found in MCC-1 type leach tests. The effect of sensitized stainless steel on the reaction is to enhance breakdown of the glass matrix thereby increasing the release of the transuranic elements from the glass. However, most of the plutonium and americium released is entrained by either the metal components of the test or by the reaction phases, and is not released to solution.

Parametric effects of glass reaction under unsaturated conditions

Eventual liquid water contact of high-level waste glass stored under the unsaturated conditions anticipated at the Yucca Mountain site will be by slow intrusion of water into a breached container/canister assembly. The water flow patterns under these unsaturated conditions will vary, and the Unsaturated Test method has been developed by the YMP to study glass reaction. The results from seven different sets of tests done to investigate the effect of systematically varying parameters, such as glass composition, composition and degree of sensitization of 304L stainless steel, water input volume, and the interval of water contact are discussed. Glass reaction has been monitored over a period of five years, and the parametric effects can result in up to a ten-fold variance in the degree of glass reaction.

Strategy for Experimental Validation of Waste Package Performance Assessment

A strategy for the experimental validation of waste package performance assessment has been developed as part of a program supported by the Repository Technology Program. The strategy was developed by reviewing the results of laboratory analog experiments, in-situ tests, repository simulation tests, and material interaction tests. As a result of the review, a listing of dependent and independent variables that influence the ingress of water into the near-field environment, the reaction between water and the waste form, and the transport of radionuclides from the near-field environment was developed. The variables necessary to incorporate into an experimental validation strategy were chosen by identifying those which had the greatest effect of each of the three major events, i.e., groundwater ingress, waste package reactions, and radionuclide transport. The methodology to perform validation experiments was examined by utilizing an existing laboratory analog approach developed for unsaturated testing of glass waste forms.