The exchange of solute mass (through molecular diffusion) between fluid in fractures and fluid in the rock matrix is called matrix diffusion. Owing to the orders-of-magnitude slower flow velocity in the matrix compared to fractures, matrix diffusion can significantly retard solute transport in fractured rock, and therefore is an important process for a variety of problems, including remediation of subsurface contamination and geological disposal of nuclear waste. The effective matrix diffusion coefficient (molecular diffusion coefficient in free water multiplied by matrix tortuosity) is an important parameter for describing matrix diffusion, and in many cases largely determines overall solute transport behavior. While matrix diffusion coefficient values measured from small rock samples in the laboratory are generally used for modeling field-scale solute transport in fractured rock (Boving and Grathwohl, 2001), several research groups recently have independently found that effective matrix diffusion coefficients much larger than laboratory measurements are needed to match field-scale tracer-test data (Neretnieks, 2002; Becker and Shapiro, 2000; Shapiro, 2001; Liu et al., 2003, 2004a). In addition to the observed enhancement, Liu et al. (2004b), based on a relatively small number of field-test results, reported that the effective matrix diffusion coefficient might be scale dependent, and, like permeability and dispersivity, …

A total system performance assessment (TSPA) model has been developed to analyze the ability of the natural and engineered barriers of the Yucca Mountain repository to isolate nuclear waste over the 10,000-year period following repository closure. The principal features of the engineered barrier system (EBS) are emplacement tunnels (or ''drifts'') containing a two-layer waste package (WP) for waste containment and a titanium drip shield to protect the waste package from seeping water and falling rock, The 20-mm-thick outer shell of the WP is composed of Alloy 22, a highly corrosion-resistant nickel-based alloy. The barrier function of the EBS is to isolate the waste from migrating water. The water and its associated chemical conditions eventually lead to degradation of the waste packages and mobilization of the radionuclides within the packages. There are five possible waste package degradation modes of the Alloy 22: general corrosion, microbially influenced corrosion, stress corrosion cracking, early failure due to manufacturing defects, and localized corrosion. This paper specifically examines the incorporation of the Alloy-22 localized corrosion model into the Yucca Mountain TSPA model, particularly the abstraction and modeling methodology, as well as issues dealing with scaling, spatial variability, uncertainty, and coupling to other sub-models that are part …

Static batch experiments were used to examine the sorption of dissolved perrhenate [Re(VII)], as a surrogate for pertechnetate [Tc(VII)], on corrosion products of A-516 carbon steel coupons contacted with synthetic groundwater or dilute water. After 109 days of contact time, the concentration of dissolved Re(VII) in the synthetic groundwater matrix decreased by approximately 26%; the dilute water matrix experienced a 99% decrease in dissolved Re(VII) over the same time period. Bulk XRD results for the corroded steel coupons showed that the corrosion products consisted primarily of maghemite, lepidocrocite, and goethite. Analyses of the coupons by SEM/EDS indicated that Re was present with the morphologically complex assemblages of Fe oxide/hydroxide corrosion products for samples spiked with the highest dissolved Re(VII) concentration (1.0 mmol/L) used for these experiments. Analyses of corroded steel coupons contacted with solutions containing 1.0 mmol/L Re(VII) by synchrotron-based methods confirmed the presence of Re sorbed with the corrosion product on the steel coupons. Analyses showed that the Re sorbed on these corroded coupons was in the +7 oxidation state, suggesting that the Re(VII) uptake mechanism did not involve reduction of Re to a lower oxidation state, such as +4. The results of our studies using Re(VII) as an …

Modeling of the alpha, beta, and gamma dose from spent fuel as a function of particle size and fuel to water ratio was examined. These doses will be combined with modeling of G values and interactions to determine the concentration of various species formed at the fuel water interface and their affect on dissolution rates.

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It is well known that the structure and properties ofdiamond-like carbon, and in particular the sp3/sp2 ratio, can becontrolled by the energy of the condensing carbon ions or atoms. In manypractical cases, the energy of ions arriving at the surface of thegrowing film is determined by the bias applied to the substrate. The biascauses a sheath to form between substrate and plasma in which thepotential difference between plasma potential and surface potentialdrops. In this contribution, we demonstrate that the same results can beobtained with grounded substrates by shifting the plasma potential. This"plasma biasing" (as opposed to "substrate biasing") is shown to workwell with pulsed cathodic carbon arcs, resulting in tetrahedral amorphouscarbon (ta-C) films that are comparable to the films obtained with theconventional substrate bias. To verify the plasma bias approach, ta-Cfilms were deposited by both conventional and plasma bias andcharacterized by transmission electron microscopy (TEM) and electronenergy loss spectrometry (EELS). Detailed data for comparison of thesefilms are provided.

Static batch experiments were used to examine the sorption of dissolved perrhenate [Re(VII)], as a surrogate for pertechnetate [Tc(VII)], on corrosion products of A-516 carbon steel coupons contacted with synthetic groundwater or dilute water. After 109 days of contact time, the concentration of dissolved Re(VII) in the synthetic groundwater matrix decreased by approximately 26%; the dilute water matrix experienced a 99% decrease in dissolved Re(VII) over the same time period. Bulk x-ray diffraction (XRD) results for the corroded steel coupons showed that the corrosion products consisted primarily of maghemite, lepidocrocite, and goethite. Analyses of the coupons by scanning electron microscopy/energy dispersive spectroscopy (SEM/EDS) indicated that Re was present with the morphologically complex assemblages of Fe oxide/hydroxide corrosion products for samples spiked with the highest dissolved Re(VII) concentration (1.0 mmol/L) used for these experiments. Analyses of corroded steel coupons contacted with solutions containing 1.0 mmol/L Re(VII) by synchrotron-based methods confirmed the presence of Re sorbed with the corrosion product on the steel coupons. Analyses showed that the Re sorbed on these corroded coupons was in the +7 oxidation state, suggesting that the Re(VII) uptake mechanism did not involve reduction of Re to a lower oxidation state, such as +4. The results …

X-ray magnetic linear dichroism at the Fe L{sub 2,3} edges of the ferrimagnet Fe{sub 3}O{sub 4} was found to exhibit a strong dependence on the relative orientation of external magnetic field, x-ray polarization, and crystalline axes. Spectral shape and magnitude of the effect were determined for Fe{sub 3}O{sub 4}(011) and Fe{sub 3}O{sub 4}(001) thin films varying the in-plane orientation of field and polarization. All dichroism spectra can be described as a linear combination of three fundamental spectra which in turn give a good agreement with calculated spectra using atomic multiplet theory. The angular dependence of the magnetic dichroism reflects the crystal field symmetry. It can be used to estimate the crystal field splitting and allows determining the spin quantization axis.

A number of tests were performed to acquire contact angles between Yucca Mountain welded tuff from Topopah Springs Lower Lithophysal geologic unit and various brine solutions. The tests were performed on core disks received from Sample Management Facility (SMF), oven dried to a constant weight and the core disks vacuum saturated in: distilled water, J-13 water, calcium chloride brine and sodium chloride brine to constant weight. The contact angles were acquired from eight points on the surface of the core disks, four on rough surface, and four on polished surface. The contact angle was measured by placing a droplet of the test fluid, distilled water, J-13 water, calcium chloride brine and sodium chloride brine on the core disks. The objective of this test was to acquire contact angles as a potential input to estimating capillary forces in accumulated dust on the waste packages and drip shields slated for the proposed High-Level Radioactive Waste Repository at Yucca Mountain, Nevada. It was noted that once the droplet contacts the test surface, it continues to spread hence the contact angle continues to decrease with elapsed time. The maximum observed angle was at time 0 or when the drop contacted the rock surface. The …