[en] This paper describes experimental work conducted to establish the chemical composition of water which will have reacted with Topopah Spring Member tuff prior to contact with waste packages. The experimental program to determine the behavior of spent fuel and borosilicate glass in the presence of this water is then described. Preliminary results of experiments using spent fuel segments with defects in the Zircaloy cladding are presented. Some results from parametric testing of a borosilicate glass with tuff and 304L stainless steel are also discussed. Experiments conducted using Topopah Spring tuff and J-13 well water have been conducted to provide an estimate of the post-emplacement environment for waste packages in a repository at Yucca Mountain. The results show that emplacement of waste packages should cause only small changes in the water chemistry and rock mineralogy. The changes in environment should not have any detrimental effects on the performance of metal barriers or waste forms. The NNWSI waste form testing program has provided preliminary results related to the release rate of radionuclides from the waste package. Those results indicate that release rates from both spent fuel and borosilicate glass should be below 1 part in 10⁵ per year. Future testing will be directed toward making release rate testing more closely relevant to site specific conditions. 17 references, 7 figures

[en] The waste acceptance specifications presented in this document represent the first stage of the Nevada Nuclear Waste Storage Investigations Project effort to establish specifications for the acceptance of waste forms for disposal at a nuclear waste repository in Yucca Mountain tuff. The only waste forms that will be dealt with in this document are the reprocessed waste forms resulting from solidification of the Savannah River Plant defense high level waste and the West Valley high level wastes. Specifications for acceptance of spent fuel will be covered in a separate document

[en] Performance assessment calculations are required for high level waste repositories for a period of 10,000 years. The Siting Guidelines require a comparison of sites following site characterization and prior to final site selection to be made over a 100,000 year period. To perform the required calculations, a detailed knowledge of the physical and chemical processes that affect waste form performance will be needed for each site. This paper will review the factors that affect the release of radionuclides from spent fuel under repository conditions, summarize our present state of knowledge, and suggest areas where more work is needed to support the performance assessment calculations. 17 refs., 5 figs., 3 tabs

[en] Samples of Topopah Spring tuff selected from vertical drill holes USW G-1, GU-3, and G-4, and from the horizontal air-drilled hole at Fran Ridge were reacted with J-13 water at 150⁰C. The primary purpose of these experiments was to compare the resulting solution chemistries to estimate the degree of homogeneity that might be expected in thermally affected ground water in a potential nuclear waste repository at Yucca Mountain. The second purpose was to relate data obtained from welded devitrified Topopah Spring tuff collected from the potential repository depth to that previously obtained using outcrop samples. The results show very similar aqueous phase chemistries for all samples after reaction for times up to 70 days. The largest difference in final solution concentrations was for silica in one of the samples from Fran Ridge. All vertical drill core samples gave results for silica that were in agreement to within +-6 ppM and indicated solubility controlled by cristobalite. The results for reaction at 150⁰C are in agreement with those obtained in previous experiments using surface outcrop samples from Fran Ridge. The major difference between the drill core results and the outcrop samples is found in the data for room-temperature rinse solutions. The outcrop samples show relatively large amounts of soluble salts that can be easily removed at room temperature. The data for room-temperature rinsing of drill core samples show no significant quantities of readily soluble salts. This result is particularly significant for the samples from the air-drilled hole at Fran Ridge, since drilling fluid that might have removed soluble salts was not used in the portion of the hole from which the samples were obtained. This result strongly suggests that the presence of soluble salts is a surface evaporation phenomenon, and that such materials are unlikely to be present at the depth of the repository

[en] As part of the Nevada Nuclear Waste Storage Investigations Project, the Lawrence Livermore National Laboratory is responsible for the design and testing of waste packages suitable for use in the Topopah Spring tuff at Yucca Mountain. Definition of the physical and chemical environment of the waste package is part of that task. This report describes a series of hydrothermal experiments using crushed tuff from the Topopah Spring Member and natural groundwater from Well J-13. The purpose of these experiments is to define the changes in water chemistry that would result from temperature changes caused by emplacement of high-level nuclear waste in a repository in the Topopah Spring tuff. Experiments were conducted at 90⁰C and at 150⁰C in Teflon-lined reaction vessels. Results are given for four rock-to-water ratios at 90⁰C and for reaction times up to 72 days. Data for 150⁰C cover reaction times up to 64 days and four rock-to-water ratios. The composition of evaporite deposits contained in the pores of surface outcrop rock material used in these experiments is determined and for two of the data sets rock material was pretreated to remove this calishe-type material. The main conclusion that can be drawn from this work is that changes in the water chemistry due to heating of the rock-water system can be expected to be very minor. There is no significant source of anions (F^-, Cl^-, NO₃^-, or SO₄/sup =/) in the rock; solution anion compositions after reaction of pretreated rock with J-13 water differ very little from the starting compositions. The major changes in cations are an increase in silica to approximately the level of cristobalite solubility, supersaturation of aluminum followed by slow precipitation, and fairly rapid precipitation of Ca and Mg due to retrograde solubility of calcite. 7 references, 7 figures, 54 tables

[en] A waste form testing program has been developed to ensure that the release rate of radionuclides from the engineered barrier system will meet NRC and EPA regulatory requirements. Waste form performance testing will be done under unsaturated, low water availability conditions which represent the expected repository conditions. Testing will also be done under conditions of total immersion of the waste form in repository-type water to cover the possibility that localized portions of the repository might contain standing water. Testing of reprocesses waste forms for CHLW and DHLW will use reaction vessels fabricated from Topopah Spring tuff. Chemical elements which are expected to show the highest release rates in the mildly oxidizing environment of the Topopah Spring tuff horizon at Yucca Mountain are Np and Tc. To determine the effect of residual canister material and of corrosion products from the canister/overpack, waste form testing will be done in the presence of these materials. The release rate of all radionuclides which are subject to NRC and EPA regulations will be measured, and the interactive effects of the released radionuclide and the rock reaction vessels will be determined. The testing program for spent fuel will determine the release rate from bare spent fuel pellets and from Zircaloy clad spent fuel where the cladding contains minor defects. A metal testing program for Zircaloy will establish the expected lifetime of the cladding material. Estimation of the state of cladding for fuel presently in reactor pool storage will provide baseline data for Zircaloy containment credit. 9 references, 4 figures

[en] A series of experiments was conducted on crushed tuff at 90⁰C and 150⁰C and on core wafer samples at 150⁰C. The results show the following: increasing the ratio of rock to water increases the rate of approach to steady-state concentrations in solution. Surface outcrop samples of Bullfrog tuff contain a minor component of highly soluble material believed to be a residue from the evaporation of surface runoff water in the pores of the rock. This material can be removed by shaking the crushed rock with water at room temperature and subjecting it briefly to heat with fresh water. Solution analyses for unfiltered samples that have reacted for short periods show higher concentrations of Al and Fe than do analyses for filtered samples; results for other elements are independent of filtration. This difference probably exists because of particulate matter in the solutions that dissolves when the samples are acidified prior to analysis. Agitation of samples during reaction produces sub-0.1 μ particles in the solutions. These particles dissolve when samples are acidified, resulting in abnormally high concentration values for some elements, such as Al and Fe. Comparison of the results for crushed rock with those for core wafers shows that the method of sample preparation does not have a large effect on the results of rock-water interaction studies

[en] In the early 1980s, tests of the leaching behavior of spent light water reactor fuel were conducted in Sweden by SKB and in the USA by the NNWSI Project. Both organizations used fuels with similar burnup, leaching solutions with similar chemical compositions, and conducted the tests at ambient hot cell temperature. Most of the test results were closely similar. The exception was in the recovery of actinide elements at the end of leaching cycles. In the NNWSI tests, the test vessels were stripped with nitric acid at the end of the leaching cycle. When the actinide inventories recovered in the original leaching cycle plus vessel rinse solutions were added to the amount recovered from the acid stripping, the relative abundances of uranium, plutonium, and other actinides were approximately the same as their inventories in the fuel samples. In the SKB tests, the materials recovered from stripping the leaching vessels were low in amount and interpreted to be fine fuel fragments. Only a few percent of the plutonium inventory that would correspond to the uranium recovered in solution was accounted for in the solution samples. To investigate the reasons for this difference in recovery of the actinides, a new test was undertaken using a fuel sample that had been leached for several years using the SKB methods. The fuel was removed from the cladding after a total of a bit more than two years of leaching inside the cladding. The bare fuel was then leached for several cycles using a geometry that simulated the NNWSI tests and a test procedure that was similar to that used in the NNWSI tests. The cladding from which the fuel was removed was also leached in a separate vessel in parallel with the bare fuel leaching. This paper presents the results of the test series and discusses the effects of specimen geometry on the mobility of actinides during leaching. During leaching of spent fuel inside the original cladding, a secondary phase containing Pu seems to form. This phase appears to be less easily dissolved than spent fuel itself

[en] The Lawrence Livermore National Laboratory (LLNL), Livermore, Calif., has been given the task of designing and verifying the performance of waste packages for the Nevada Nuclear Waste Storage Investigations (NNWSI) Project. NNWSI is studying the suitability of the tuffaceous rocks at Yucca Mountain, Nevada Test Site, for the potential construction of a high-level nuclear waste repository. This report gives a summary description of the three waste forms for which LLNL is designing waste packages: spent fuel, either as intact assemblies or as consolidated fuel pins, reprocessed commercial high-level waste in the form of borosilicate glass, and reprocessed defense high-level waste from the Defense Waste Processing Facility in Aiken, S.C. Reference packing material for use with the alternative waste package design for spent fuel is also described. 14 references, 8 figures, 20 tables

[en] This report describes a series of hydrothermal experiments using crushed tuff from the Topopah Spring Member and natural ground water from well J-13. The purpose of these experiments is to define the changes in water chemistry that would result from temperature changes caused by emplacing high-level nuclear waste in a repository in the Topopah Spring tuff. Experiments were conducted at 120⁰C in Teflon-lined reaction vessels at four separate rock-to-water ratios and for reaction times up to 72 days. The composition of evaporite deposits contained in the pores of the surface-outcrop rock material used in these experiments is determined from solution compositions resulting from treatment of the rock before the start of the experiments. Results from the experiments at 120⁰C are compared with previous experimental results from hydrothermal reaction of the Topopah Spring tuff with J-13 water at 90 and 150⁰C. The main conclusion that can be drawn from this work is that changes in the water chemistry due to heating of the rock-water system can be expected to be very minor. There is no significant source of anions (F^-, Cl^-, NO₃^-, or SO₄^2-) in the rock; solution anion compositions after reaction of pretreated rock with J-13 water differ very little from the starting compositions. The major changes in cations are an increase in silica to approximately the level of cristobalite solubility, supersaturation of aluminum followed by slow precipitation, and fairly rapid precipitation of calcium and magnesium due to the retrograde solubility of calcite. These results are in good agreement with those previously reported for reaction of the tuff with J-13 water at 90 and 150⁰C. 7 references, 7 figures, 28 tables