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Pitting corrosion was evaluated on stainless steels 304H, 304, and 316L the surfaces of which had ASTM seawater printed on them as a function of surface roughness after exposure to an exemplar realistic atmospheric diurnal cycle for up to one year. Methods to evaluate pitting damage included optical imaging, scanning electron microscopy imaging, profilometry analysis, and polarization scans. The developed cyclic exposure environment did not significantly influence pitting morphology nor depth in comparison to prior static exposure environments. Cross-hatching was observed in a majority of pits for all material compositions with the roughest surface finish (#4 finish) and in all surface finishes for the 304H composition. Evidence is provided that cross-hatched pit morphologies are caused by slip bands produced during the grinding process for the #4 finish or by material processing. Additionally, micro-cracking was observed in pits formed on samples with the #4 surface finish and was greatly reduced or absent for pits formed on samples with smooth surface finishes. This suggests that both a low RH leading to an MgCl2-dominated environment and a rough surface containing significant residual stress are necessary for micro-cracking. Finally, the use of various characterization techniques and cross sectioning was employed to both qualitatively and quantitatively assess pitting damage across all SS compositions and surface finishes.

The purpose of this report (REV04) is to document the thermal-hydrologic-chemical (THC) seepage model, which simulates the composition of waters that could potentially seep into emplacement drifts, and the composition of the gas phase. The THC seepage model is processed and abstracted for use in the total system performance assessment (TSPA) for the license application (LA). This report has been developed in accordance with ''Technical Work Plan for: Near-Field Environment and Transport: Coupled Processes (Mountain-Scale TH/THC/THM, Drift-Scale THC Seepage, and Post-Processing Analysis for THC Seepage) Report Integration'' (BSC 2005 [DIRS 172761]). The technical work plan (TWP) describes planning information pertaining to the technical scope, content, and management of this report. The plan for validation of the models documented in this report is given in Section 2.2.2, ''Model Validation for the DS THC Seepage Model,'' of the TWP. The TWP (Section 3.2.2) identifies Acceptance Criteria 1 to 4 for ''Quantity and Chemistry of Water Contacting Engineered Barriers and Waste Forms'' (NRC 2003 [DIRS 163274]) as being applicable to this report; however, in variance to the TWP, Acceptance Criterion 5 has also been determined to be applicable, and is addressed, along with the other Acceptance Criteria, in Section 4.2 of this report.more » Also, three FEPS not listed in the TWP (2.2.10.01.0A, 2.2.10.06.0A, and 2.2.11.02.0A) are partially addressed in this report, and have been added to the list of excluded FEPS in Table 6.1-2. This report has been developed in accordance with LP-SIII.10Q-BSC, ''Models''. This report documents the THC seepage model and a derivative used for validation, the Drift Scale Test (DST) THC submodel. The THC seepage model is a drift-scale process model for predicting the composition of gas and water that could enter waste emplacement drifts and the effects of mineral alteration on flow in rocks surrounding drifts. The DST THC submodel uses a drift-scale process model relying on the same conceptual model and many of the same input data (i.e., physical, hydrologic, thermodynamic, and kinetic) as the THC seepage model. The DST THC submodel is the primary means for validating the THC seepage model. The DST THC submodel compares predicted water and gas compositions, and mineral alteration patterns, with observed data from the DST. These models provide the framework to evaluate THC coupled processes at the drift scale, predict flow and transport behavior for specified thermal-loading conditions, and predict the evolution of mineral alteration and fluid chemistry around potential waste emplacement drifts. The DST THC submodel is used solely for the validation of the THC seepage model and is not used for calibration to measured data.« less

This report attempts to describe the geochemical foundations of the behavior of radionuclides in the environment. The information is obtained and applied in three interacting spheres of inquiry and analysis: (1) experimental studies and theoretical calculations, (2) field studies of contaminated and natural analog sites and (3) model predictions of radionuclide behavior in remediation and waste disposal. Analyses of the risks from radioactive contamination require estimation of the rates of release and dispersion of the radionuclides through potential exposure pathways. These processes are controlled by solubility, speciation, sorption, and colloidal transport, which are strong functions of the compositions of the groundwater and geomedia as well as the atomic structure of the radionuclides. The chemistry of the fission products is relatively simple compared to the actinides. Because of their relatively short half-lives, fission products account for a large fraction of the radioactivity in nuclear waste for the first several hundred years but do not represent a long-term hazard in the environment. The chemistry of the longer-lived actinides is complex; however, some trends in their behavior can be described. Actinide elements of a given oxidation state have either similar or systematically varying chemical properties due to similarities in ionic size, coordination number, valence, and electron structure. In dilute aqueous systems at neutral to basic pH, the dominant actinide species are hydroxy- and carbonato-complexes, and the solubility-limiting solid phases are commonly oxides, hydroxides or carbonates. In general, actinide sorption will decrease in the presence of ligands that complex with the radionuclide; sorption of the (IV) species of actinides (Np, Pu, U) is generally greater than of the (V) species. The geochemistry of key radionuclides in three different environments is described in this report. These include: (1) low ionic strength reducing waters from crystalline rocks at nuclear waste research sites in Sweden; (2) oxic water from the J-13 well at Yucca Mountain, Nevada, the site of a proposed repository for high level nuclear waste (HLW) in tuffaceous rocks; and (3) reference brines associated with the Waste Isolation Pilot Plant (WIPP). The transport behaviors of radionuclides associated with the Chernobyl reactor accident and the Oklo Natural Reactor are described. These examples span wide temporal and spatial scales and include the rapid geochemical and physical processes important to nuclear reactor accidents or industrial discharges as well as the slower processes important to the geologic disposal of nuclear waste. Application of geochemical information to remediating or assessing the risk posed by radioactive contamination is the final subject of this report. After radioactive source terms have been removed, large volumes of soil and water with low but potentially hazardous levels of contamination may remain. For poorly-sorbing radionuclides, capture of contaminated water and removal of radionuclides may be possible using permeable reactive barriers and bioremediation. For strongly sorbing radionuclides, contaminant plumes will move very slowly. Through a combination of monitoring, regulations and modeling, it may be possible to have confidence that they will not be a hazard to current or future populations. Abstraction of the hydrogeochemical properties of real systems into simple models is required for probabilistic risk assessment. Simplifications in solubility and sorption models used in performance assessment calculations for the WIPP and the proposed HLW repository at Yucca Mountain are briefly described.

A processed quartz sand (Wedron 510), mined from the St. Peter sandstone, has been characterized by a variety of chemical and physical methods for use as a reference porous media in transport model validation experiments. Wedron 510 sand was used in an intermediate-scale experiment involving migration of Ni, Li and Br through a 6-m high x 3-m diameter caisson. Ni and Li adsorption/desorption, and Li/Ni site-competition experiments yielded information on the importance of the trace mineral phases to adsorption of Li and Ni by the sand. The presence of an iron hydroxide coating similar to goethite on the sand grains is suggested by visual observation and leaching experiments. Kaolinite was identified by SEM and XRD as a significant trace mineral phase in the sand and occurs as small particles coating the sand grains. Quartz, the predominant constituent of the sand by weight, does not appear to contribute significantly to the adsorption properties of the sand. Qualitatively, the adsorption properties of the sand can be adequately modeled as a two-mineral system (goethite and kaolinite). The studies described in this report should provide a basis for understanding transport of Ni, Li and Br through porous media similar to the reference sand. Techniques were developed for obtaining parameter values for surface complexation and kinetic adsorption models for the sand and its mineral components. These constants can be used directly in coupled hydrogeochemical transport codes. The techniques should be useful for characterization of other natural materials and elements in high-level nuclear waste in support of coupled hydrogeochemical transport calculations for Yucca Mountain.