Roberto T. Pabalan

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.

Uranium(6+) sorption on montmorillonite: Experimental and surface complexation modeling study

Sorption interactions with montmorillonite and other clay minerals in soils, sediments, and rocks are potentially important mechanisms for attenuating the mobility of U(6+) and other radionuclides through the subsurface environment. Batch experiments were conducted (in equilibrium with atmospheric % MathType!MTEF!2!1!+-% feaafeart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXafv3ySLgzGmvETj2BSbqefm0B1jxALjhiov2D% aebbfv3ySLgzGueE0jxyaibaiiYdd9qrFfea0dXdf9vqai-hEir8Ve% ea0de9qq-hbrpepeea0db9q8as0-LqLs-Jirpepeea0-as0Fb9pgea% 0lrP0xe9Fve9Fve9qapdbaqaaeGacaGaaiaabeqaamaabaabcaGcba% acbiGaiWiG-bfadaWgaaWcbaacbaGaa43qaiaa+9eadaWgaaqaaiaa% +jdaaWqabaaaleqaaaaa!400D!\[P_{CO_2 } \])to determine the effects of varying pH (2 to 9), solid-mass to solution-volume ratio (M/V = 0.028 to 3.2 g/L), and solution concentration (2 × 10−7 and 2 × 10−6 M 233U) on U(6+) sorption on SAz-1 montmorillonite. The study focused on U(6+) surface complexation on hydroxylated edge sites as the sorption mechanism of interest because it is expected to be the predominant sorption mechanism at pHs typical of natural waters (pH ≈6 to ≈9). Thus, the experiments were conducted with a 0.1 M NaNO3 matrix to suppress ion-exchange between U(6+) in solution and interlayer cations. The results show that U(6+) sorption on montmorillonite is a strong function of pH, reaching a maximum at near-neutral pH (≈6 to ≈6.5) and decreasing sharply towards more acidic or more alkaline conditions. A comparison of the pH-dependence of U(6+) sorption with that of U(6+) aqueous speciation indicates a close correspondence between U(6+) sorption and the predominance field of U(6+)-hydroxy complexes. At high pH, sorption is inhibited due to formation of aqueous U(6+)-carbonate complexes. At low pH, the low sorption values indicate that the 0.1 M NaNO3 matrix was effective in suppressing ion-exchange between the uranyl (UO22+) species and interlayer cations in montmorillonite. At pH and carbonate concentrations typical of natural waters, sorption of U(6+) on montmorillonite can vary by four orders of magnitude and can become negligible at high pH.The experimental results were used to develop a thermodynamic model based on a surface complexation approach to permit predictions of U(6+) sorption at differing physicochemical conditions. A Diffuse-Layer model (DLM) assuming aluminol (>AlOHℴ) and silanol (>SiOHℴ) edge sites and two U(6+) surface complexation reactions per site effectively simulates the complex sorption behavior observed in the U(6+)-H2O-CO2-montmorillonite system at an ionic strength of 0.1 M and pH > 3.5. A comparison of model predictions with data from this study and from published literature shows good agreement and suggests that surface complexation models based on parameters derived from a limited set of data could be useful in extrapolating radionuclide sorption over a range of geochemical conditions. Such an approach could be used to support transport modeling by providing a better alternative to the use of constant Kds in transport 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).

URANYL SURFACE COMPLEXES IN A MIXED-CHARGE MONTMORILLONITE: MONTE CARLO COMPUTER SIMULATION AND POLARIZED XAFS RESULTS

We report a combined experimental and theoretical study of uranyl complexes that form on the interlayer siloxane surfaces of montmorillonite. We also consider the effect of isomorphic substitution on surface complexation since our montmorillonite sample contains charge sites in both the octahedral and tetrahedral sheets. Results are given for the two-layer hydrate with a layer spacing of 14.58 Å. Polarized-dependent X-ray absorption fine structure spectra are nearly invariant with the incident angle, indicating that the uranyl ions are oriented neither perpendicular nor parallel to the basal plane of montmorillonite. The equilibrated geometry from Monte Carlo simulations suggests that uranyl ions form outer-sphere surface complexes with the [O=U=O]2+ axis tilted at an angle of ~45° to the surface normal.

Experimental and Modeling Study of Ion Exchange Between Aqueous Solutions and the Zeolite Mineral Clinoptilolite

Ion-exchange experiments were conducted at 25°C between the zeolite mineral clinoptilolite and aqueous solutions of Na+/Sr2+ (0.005, 0.05, and 0.5 N), K+/Sr2+ (0.05N), and K+/Ca2+ (0.05 N). The isotherm data were used to derive equilibrium constants and Gibbs energies for the ion-exchange reactions and Margules parameters for the zeolite solid solution. The Margules model, in combination with the Pitzer equations for activity coefficients of aqueous ions, was used to predict isotherms for ion exchange involving clinoptilolite and aqueous solutions of Na+/Sr2+, K+/Sr2+, and K+/Ca2+ over wide ranges of solution composition and concentration. The ion-exchange isotherms are strongly dependent on the total solution concentration. For Na+/Sr2+ ion exchange, isotherm values at 0.005 and 0.5 N predicted using thermodynamic parameters derived from the 0.05 N data showed excellent agreement with measured values. The model was also applied to calculations of aqueous composition based on the chemistry of coexisting zeolite phases. The results show that the aqueous composition can be predicted well from the composition of the zeolite, at least for systems that involved binary (two-cation) exchange. Because the thermodynamic model can be easily extended to ternary and more complicated mixtures, it may be useful for modeling ion-exchange equilibria in multicomponent systems.

MONTE CARLO AND MOLECULAR DYNAMICS SIMULATION OF URANYL ADSORPTION ON MONTMORILLONITE CLAY

We performed Monte Carlo and molecular dynamics simulations to investigate the interlayer structure of a uranyl-substituted smectite clay. Our clay model is a dioctahedral montmorillonite with negative charge sites in the octahedral sheet only. We simulated a wide range of interlayer water content (0 mg H2O/g clay — 260 mg H2O/g clay), but we were particularly interested in the two-layer hydrate that has been the focus of recent X-ray absorption experiments. Our simulation results for the two-layer hydrate of uranyl-montmorillonite yield a water content of 160 mg H2O/g clay and a layer spacing of 14.66 Å. Except at extremely low water content, uranyl cations are oriented nearly parallel to the surface normal in an outer-sphere complex. The first coordination shell consists of five water molecules with an average U-O distance of 2.45 Å, in good agreement with experimental data. At low water content, the cations can assume a perpendicular orientation to include surface oxygen atoms in the first coordination shell. Our molecular dynamics results show that

Abstraction of mechanistic sorption model results for performance assessment calculations at Yucca Mountain, Nevada

{\rm{U}}{{\rm{O}}_2}\left( {{{\rm{H}}_2}{\rm{O}}} \right)_5^{2 + }

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

UO2(H2O)52+ complexes translate within the clay pore through a jump diffusion process, and that first-shell water molecules are exchangeable and interchangeable.

Corrosion Behavior of Carbon Steel and Stainless Steel Materials under Salt Deposits in Simulated Dry Repository Environments

Abstract Sorption onto minerals in the geologic setting may help to mitigate potential radionuclide transport from the proposed high-level radioactive waste repository at Yucca Mountain (YM), Nevada. An approach is developed for including aspects of more mechanistic sorption models into current probabilistic performance assessment (PA) calculations. Data on water chemistry from the vicinity of YM are screened and used to calculate the ranges in 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, but the calculated range is almost five orders of magnitude for Np(V) sorption and nine orders of magnitude for U(VI) sorption. Calculated sorption parameters may also vary at a single sample location by almost a factor of 10 over time periods of the order of days to years due to changes in chemistry, although sampling and analytical methodologies may introduce artifacts that add uncertainty to the evaluation of these fluctuations. Finally, correlation coefficients 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.

Experimental Determination of the Deliquescence Relative Humidity and Conductivity of Multicomponent Salt Mixtures

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.