James D. Prikryl

Alteration of uraninite from the Nopal I deposit, Pen˜a Blanca District, Chihuahua, Mexico, compared to degradation of spent nuclear fuel in the proposed U.S. high-level nuclear waste repository at Yucca Mountain, Nevada

Abstract At the Nopal I uranium deposit, primary uraninite (nominally UO 2+ x ) has altered almost completely to a suite of secondary uranyl minerals. The deposit is located in a Basin and Range horst composed of welded silicic tuff; uranium mineralization presently occurs in a chemically oxidizing and hydrologically unsaturated zone of the structural block. These characteristics are similar to those of the proposed U.S. high-level nuclear waste (HLW) repository at Yucca Mountain, Nevada. Petrographic analyses indicate that residual Nopal I uraninite is fine grained (5–10 μm) and has a low trace element content (average about 3 wt%). These characteristics compare well with spent nuclear fuel. The oxidation and formation of secondary minerals from the uraninite have occurred in an environment dominated by components common in host rocks of the Nopal I system (e.g. Si, Ca, K, Na and H 2 O) and also common to Yucca Mountain. In contrast, secondary phases in most other uranium deposits form from elements largely absent from spent fuel and from the Yucca Mountain environment (e.g. Pb, P and V). The oxidation of Nopal I uraninite and the sequence of alteration products, their intergrowths and morphologies are remarkably similar to those observed in reported corrosion experiments using spent fuel and unirradiated UO 2 under conditions intended to approximate those anticipated for the proposed Yucca Mountain repository. The end products of these reported laboratory experiments and the natural alteration of Nopal I uraninite are dominated by uranophane [nominally Ca(UO 2 ) 2 Si 2 O 7 ·6H 2 O] with lesser amounts of soddyite [nominally (UO 2 ) 2 SiO 4 ·2H 2 O] and other uranyl minerals. These similarities in reaction product occurrence developed despite the differences in time and physical—chemical environment between Yucca Mountain-approximate laboratory experiments and Yucca Mountain-approximate uraninite alteration at Nopal I, suggesting that the results may reasonably represent phases likely to form during long-term alteration of spent fuel in a Yucca Mountain repository. From this analogy, it may be concluded that the likely compositional ranges of dominant spent fuel alteration phases in the Yucca Mountain environment may be relatively limited and may be insensitive to small variations in system conditions.

UraniumVI sorption behavior on silicate mineral mixtures.

UraniumVI sorption experiments involving quartz and clinoptilolite, important mineral phases at the proposed US nuclear waste repository at Yucca Mountain, NV, were conducted to evaluate the ability of surface complexation models to predict UVI sorption onto mineral mixtures based on parameters derived from single-mineral experiments. The experiments were conducted at an initial UVI aqueous concentration of approximately 2.0 x 10(-7) mol.l-1 (0.1 mol.l-1 NaNO3 matrix) and over the pH range approximately 2.5 to approximately 9.5. The UVI solutions were reacted with either quartz or clinoptilolite only, or with mixtures of the two minerals. The experiments were carried out under atmospheric pCO2(g) conditions (in loosely capped containers) or under limited pCO2(g) (in capped containers or in a glove box). Data from sorption experiments on quartz at atmospheric pCO2 conditions were used to derive UVI binding constants for a diffuse-layer surface complexation model (DLM). The DLM was then used with surface area as a scaling factor to predict sorption of UVI onto clinoptilolite and clinoptilolite/quartz mixtures under both atmospheric and low pCO2 conditions. The calculations reproduced many aspects of the pH-dependent sorption behavior. If this approach can be demonstrated for natural mineral assemblages, it may be useful as a relatively simple method for improving radionuclide transport models in performance-assessment calculations.

Chapter 3 – UraniumVI Sorption onto Selected Mineral Surfaces: Key Geochemical Parameters

Batch U(VI) sorption experiments were conducted using quartz, montmorillonite, clinoptilolite, and {alpha}-alumina to determine the key geochemical parameters that influence sorption onto mineral surfaces. The experiments were done at different initial U concentration, pH, M/V, and ionic strength, and at ambient and elevated PCO{sub 2} (10{sup -3.5} and 10{sup -2.0} atm, respectively). The results show that U(VI) sorption on all the minerals studied reaches a maximum at near-neutral pH ({approximately}6.3-6.8) and decreases sharply towards more acidic or alkaline conditions. The pH range where U sorption occurs corresponds to the predominance field of aqueous monomeric U(VI)-hydroxy complexes. Sorption is inhibited at high pH and PCO{sub 2} due to formation of aqueous U(VI)-carbonate complexes. For montmorillonite and clinoptilolite, ion-exchange was suppressed due to the relatively high ionic strength of the solutions. Surface charge properties of the sorbent are inferred to be relatively unimportant factors in U(VI) sorption. Sorption data plotted in terms of K{sub d} show that M/V ratio has little influence on the distribution of U(VI) between the solid and aqueous phases. Modeling of the sorption behavior of U(VI) was performed using a surface complexation approach (Diffuse-Layer Model).

Uranium transport through fractured silicic tuff and relative retention in areas with distinct fracture characteristics

Abstract The Nopal I uranium (U) deposit, in the Pefia Blanca District, Chihuahua, Mexico, has been identified as analogous in some regards to the candidate U.S. high-level waste (HLW) repository at Yucca Mountain, Nevada. Uranium transport at the Nopal I deposit has been studied to investigate mechanisms by which HLW components could be transported through silicic tuff over long time periods. This investigation focused on approximately 1400 m2 of essentially continuous bedrock outcrop spanning the Nopal I deposit and surrounding host tuff. Data collected document: (i) the distributions of U within and around the Nopal I deposit, (ii) the distribution and characteristics of the fracture network within and surrounding the deposit, and (iii) the transport of U away from the deposit mainly along fracture paths. Uranium-series isotopic measurements indicate mobilization of U along the margin of the deposit within the last 1 Ma and significant U transport at about 54 Ka. Transport of U away from the Nopal I deposit along a few relatively continuous mesofractures achieved maximum distances at least 20 times greater than transport through the general fracture network composed of thousands of less continuous microfractures within and surrounding the deposit. Uranium transport away from the deposit appears to be largely independent of variations in the general fracture network pattern. Transport of U away from individual micro- and meso-fractures into homogeneous, unfractured tuff matrix appears limited to distances less than 1 mm. At the Nopal I deposit, matrix diffusion does not appear to have been an important factor for retardation of U. This analysis suggests a ranking for U retention: (i) microfracture network retention ≫ mesofracture retention, and (ii) individual microfracture retention ≫ matrix retention.

Migration behavior of naturally occurring radionuclides at the Nopal I uranium deposit, Chihuahua, Mexico

Oxidation of pyrite at the Nopal I uranium deposit, Pena Blanca district, Chihuahua, Mexico has resulted in the formation of Fe-oxides/hydroxides. Anomalous U concentrations (i.e. several hundred to several thousand ppm) measured in goethite, hematite, and amorphous Fe-oxyhydroxides in a major fracture that crosscuts the deposit and the absence of U minerals in the fracture suggest that U was retained during secondary mineral growth or sorbed on mineral surfaces. Mobilization and transport of U away from the deposit is suggested by decreasing U concentrations in fracture-infilling materials and in goethite and hematite with distance from the deposit. Greater than unity 234U238U activity ratios measured in fracture-infilling materials indicate relatively recent ( < 1 Ma) U uptake from fluids that carried excess 234U. Systematic decreases in 234U238U activity ratios of fracture materials with distance from the deposit suggest a multistage mobilization process, such as remobilization of U from 234U-enriched infill minerals or differential or diminished transport of U-bearing solutions containing excess 234U.

Experimental study of uranium(6+) sorption of the zeolite mineral clinoptilolite

Experiments on the sorption of uranium(6+) on clinoptilolite from solutions in equilibrium with atmospheric CO{sub 2}(g) were conducted to understand the fundamental controls on uranium sorption on zeolite minerals, including the effects of pH, aqueous uranium speciation, and uranium concentration in solution. The results indicate that uranium(6+) species are strongly sorbed on the zeolite mineral clinoptilolite at near-neutral pH. The amount of uranium sorbed is strongly dependent on pH and, to some extent, on the total concentration of uranium. Uranium sorption on clinoptilolite is important in the pH range where UO{sub 2}(OH){sub 2}{degrees}(aq) is the predominant uranium aqueous species, whereas sorption is inhibited at pH`s where carbonate- and hydroxy-carbonate-complexes are the primary uranyl species. Surface adsorption appears to be the main sorption mechanism, although at pH<4 the results suggest ion exchange may occur between the UO{sub 2}{sup 2+} ions in solution and the cations in the intracrystalline cation exchange sites of clinoptilolite. The effectiveness of zeolite-rich horizons underneath Yucca Mountain, Nevada, as barriers to actinide transport through sorption processes will depend strongly on groundwater chemistry. Reliable predictions of radionuclide transport through these horizons will need to properly account for changes in solution chemistry.

Oxidative Alteration of Uraninite at the Nopal I Deposit, Mexico: Possible Contaminant Transport and Source Term Constraints for the Proposed Repository at Yucca Mountain

The Nopal I uranium deposit at Pena Blanca, Mexico is being studied as a natural analog of the proposed high-level nuclear waste repository at Yucca Mountain. Identification of secondary uranium phases at Nopal I, and the sequence of their formation after uraninite oxidation, provides insight into the source term for uranium, and suggests that uranophane may control uranium release and transport in a silici, tuffaceous, chemically oxidizing, and hydrologically unsaturated environment. Possible constraints on contaminant transport at Nopal I are derived from the spatial distribution of uranium and from measurements of {sup 238}U decay-series isotopes. The analyses indicate that flow of U-bearing fluids was influenced strongly by fracture density, but that the flow of these fluids was not restricted to fractures. Gamma spectroscopic measurements of {sup 238}U decay-series isotopes indicates secular equilibrium, which suggests undetectable U transport under present conditions.

Sorption of uranium(6+) and neptunium(5+) by surfactant-modified natural zeolites

Experiments were conducted to determine the ability of surfactant-modification to enhance the ability of natural zeolites to sorb U(6+) and Np(5+). Natural zeolite material, comprised mainly of clinoptilolite and treated with the cationic surfactant hexadecyltrimethylammonium-bromide (HDTMA), was reacted with U(6+) and Np(5+) solutions open to the atmosphere and having a range of radionuclide concentration, pH, and NaCl concentration. The results indicate surfactant-modification of the zeolite enhances its ability to sorb U(6+), particularly at pHs greater than six where U(6+) sorption on unmodified zeolite is typically low due to formation of anionic U(6+) aqueous carbonate complexes. In contrast, there is little enhancement of Np(5+) sorption onto surfactant-modified zeolite. The presence of chloride anions in solution makes surfactant-modification less effective. The enhanced sorption of U(6+) is interpreted to be due to anion exchange with counterions on the external portion of a surfactant bilayer or admicelles.

A test of long-term, predictive, geochemical transport modeling at the Akrotiri archaeological site

Abstract A study of elemental transport at the Akrotiri archeological site on the island of Santorini, Greece, has been conducted to evaluate the use of natural analog data in support of long-term predictive modeling of the performance of a proposed geologic repository for nuclear waste at Yucca Mountain, Nevada. Akrotiri and Yucca Mountain have many analogous features including silicic volcanic rocks, relatively dry climates, and oxidizing, hydrologically unsaturated subsurface conditions. Transport of trace elements from artifacts buried in volcanic ash 3600 years ago at Akrotiri is analogous to transport of radioactive wastes in the proposed repository. Subtle evidence for a plume of Cu, Zn, and Pb has been detected by selective leaching of packed earth and bedrock samples collected immediately beneath the site where bronze and lead artifacts were excavated. The geologic setting of the artifacts and the hydraulic properties of the enclosing media were characterized. A numerical model of the type used in repository performance assessments was developed for elemental transport at the site. Site characterization data were used to build the model but no prior information on the nature of the contaminant plume was provided to the modelers. Some model results are qualitatively consistent with field data, including the small amount of material transported, limited amounts of sorbed material, and relatively elevated sorption on a packed earth layer, However, discrepancies result from incomplete representation of heterogeneity and complexity and poorly constrained model parameters. Identification of such system characteristics and model limitations in relevant systems is a major contribution that analog studies can contribute in support of repository modeling.

Radionuclide Sorption at Yucca Mountain, Nevada - A Demonstration of an Alternative Approach for Performance Assessment

An approach is developed for including aspects of mechanistic models of radionuclide sorption into performance assessment (PA) calculations. Water chemistry data from the vicinity of Yucca Mountain (YM), Nevada are screened and used to calculate the ranges in key parameters that could exert control on radionuclide sorption behavior. Using a diffuse-layer surface complexation model, sorption parameters for Np(V) and U(VI) are calculated based on the chemistry of each water sample. Model results suggest that lognormal probability distribution functions (PDFs) of sorption parameters are appropriate for most of the samples; the total calculated range is almost five orders of magnitude for Np(V) sorption and nine orders of magnitude for U(VI) sorption, but most samples fall in a narrower range. Finally, statistical correlation between the calculated Np(V) and U(VI) sorption parameters can be included as input into PA sampling routines, so that the value selected for one radionuclide sorption parameter is conditioned by its statistical relationship to the others. The approaches outlined here can be adapted readily to current PA efforts, using site-specific information to provide geochemical constraints on PDFs for radionuclide transport parameters.