136 research outputs found
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Nickel and manganese interaction with calcite
Many divalent metal cations sorb to calcite surfaces and incorporate into calcite to varying degrees. Since calcite may sorb trace elements in the environment, the factors controlling metal-calcite interactions are critical to understanding element cycling. The interaction of divalent metal cations with calcite can be critical to toxic metal immobilization, nutrient cycling, interpretation of past redox conditions, tracing fluid flow, for example. Sorption of Ni and Mn on calcite surfaces was studied by Zachara et al.. At any particular pH, the sorption of Mn on calcite was greater than Ni. This was attributed in part to the similarity of divalent Mn and Ca with respect to ion size. Although direct spectroscopic evidence was not available, sorption/desorption results suggested that Mn quickly forms a surface precipitate or solid solution while Ni forms a hydrated surface complex that may incorporate into calcite much more slowly via recrystallization. Because Mn(II) ionic radius is similar to that of Ca(II) (0.80 versus 1.0{angstrom}), and because MnCO{sub 3} has a structure similar to calcite, it is likely that Mn can substitute directly for Ca in the calcite structure. The ionic radius of Ni(II) is significantly smaller (0.69{angstrom}) and Ni(OH){sub 2} precipitation is likely to be favored in most systems. For Ni, direct substitution for Ca is less likely or may require more significant calcite lattice deformation
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Summary of Radionuclide Reactive Transport Experiments in Fractured Tuff and Carbonate Rocks from Yucca Flat, Nevada Test Site
In the Yucca Flat basin of the Nevada Test Site (NTS), 747 shaft and tunnel nuclear detonations were conducted primarily within the tuff confining unit (TCU) or the overlying alluvium. The TCU in the Yucca Flat basin is hypothesized to inhibit radionuclide migration to the highly transmissive and regionally extensive lower carbonate aquifer (LCA) due to its wide-spread aerial extent, low permeability, and chemical reactivity. However, fast transport pathways through the TCU by way of fractures may provide a migration path for radionuclides to the LCA. Radionuclide transport in both TCU and the LCA fractures is likely to determine the location of the contaminant boundary for the Yucca Flat/Climax Mine Corrective Action Unit (CAU). Radionuclide transport through the TCU may involve both matrix and fracture flow. However, radionuclide migration over significant distances is likely to be dominated by fracture transport. Transport through the LCA will almost certainly be dominated by fracture flow, as the LCA has a very dense, low porosity matrix with very low permeability. Because of the complex nature of reactive transport in fractures, a stepwise approach to identifying mechanisms controlling radionuclide transport was used. The simplest LLNL experiments included radionuclide transport through synthetic parallel-plate fractured tuff and carbonate cores. These simplified fracture transport experiments isolated matrix diffusion and sorption effects from all other fracture transport processes (fracture lining mineral sorption, heterogeneous flow, etc.). Additional fracture transport complexity was added by performing induced fractured LCA flowthrough experiments (effect of aperture heterogeneity) or iron oxide coated parallel plate TCU flowthrough experiments (effect of fracture lining minerals). Finally naturally fractured tuff and carbonate cores were examined at LLNL and LANL. All tuff and carbonate core used in the experiments was obtained from the USGS Core Library, Mercury, Nevada. Readers are referred to the original reports ''Radionuclide Transport in Tuff and Carbonate Fractures from Yucca Flat, Nevada Test Site'' (Zavarin et al., 2005) and ''Radionuclide Sorption and Transport in Fractured Rocks of Yucca Flat, Nevada Test Site'' (Ware et al., 2005) for specific details not covered in this summary report
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Spatial Variability of Reactive Mineral and Radionuclide Kd Distributions in the Tuff Confining Unit: Yucca Flat, Nevada Test Site
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Np and Pu Sorption to Manganese Oxide Minerals
Manganese oxide minerals are a significant component of the fracture lining mineralogy at Yucca Mountain (Carlos et al., 1993) and within the tuff-confining unit at Yucca Flat (Prothro, 1998), Pahute Mesa (Drellack et al., 1997), and other locations at the Nevada Test Site (NTS). Radionuclide sorption to manganese oxide minerals was not included in recent Lawrence Livermore National Laboratory (LLNL) hydrologic source term (HST) models which attempt to predict the migration behavior of radionuclides away from underground nuclear tests. However, experiments performed for the Yucca Mountain Program suggest that these minerals may control much of the retardation of certain radionuclides, particularly Np and Pu (Triay et al., 1991; Duff et al., 1999). As a result, recent HST model results may significantly overpredict radionuclide transport away from underground nuclear tests. The sorption model used in HST calculations performed at LLNL includes sorption to iron oxide, calcite, zeolite, smectite, and mica minerals (Zavarin and Bruton 2004a; 2004b). For the majority of radiologic source term (RST) radionuclides, we believe that this accounts for the dominant sorption processes controlling transport. However, for the case of Np, sorption is rather weak to all but the iron and manganese oxides (Figure 1). Thus, we can expect to significantly reduce predicted Np transport by accounting for Np sorption to manganese oxides. Similarly, Pu has been shown to be predominantly associated with manganese oxides in Yucca Mountain fractured tuffs (Duff et al., 1999). Recent results on colloid-facilitated Pu transport (Kersting and Reimus, 2003) also suggest that manganese oxide coatings on fracture surfaces may compete with colloids for Pu, thus reducing the effects of colloid-facilitated Pu transport (Figure 1b). The available data suggest that it is important to incorporate Np and Pu sorption to manganese oxides in reactive transport models. However, few data are available for inclusion in our model. A survey of published data found only single-point (Triay et al., 1991; Kersting and Reimus, 2003; Keeney-Kennicutt and Morse, 1984; 1985) and qualitative (Duff et al., 1999; Dyer et al., 2000a; 2000b) Np and Pu sorption information. This report describes recent experiments that quantified the sorption and desorption of Np(V) and Pu(IV) onto three manganese oxide minerals as a function of pH and time. The three manganese oxides (pyrolusite, birnessite, and hollandite) have all been observed on fracture surfaces at Yucca Mountain and are likely to predominate at the NTS. Pyrolusite, birnessite, and hollandite comprise both a range of manganese oxide structure (framework, layered, and tunnel, respectively) and composition and a range of observed manganese oxide mineralogies. The pH range of 3-10 used in these experiments covers the range of pH observed in NTS groundwater (Rose et al., 1997)
Development of a Composite Non-Electrostatic Surface Complexation Model Describing Plutonium Sorption to Aluminosilicates
Due to their ubiquity in nature and chemical reactivity, aluminosilicate minerals play an important role in retarding actinide subsurface migration. However, very few studies have examined Pu interaction with clay minerals in sufficient detail to produce a credible mechanistic model of its behavior. In this work, Pu(IV) and Pu(V) interactions with silica, gibbsite (Aloxide), and Na-montmorillonite (smectite clay) were examined as a function of time and pH. Sorption of Pu(IV) and Pu(V) to gibbsite and silica increased with pH (4 to 10). The Pu(V) sorption edge shifted to lower pH values over time and approached that of Pu(IV). This behavior is apparently due to surface mediated reduction of Pu(V) to Pu(IV). Surface complexation constants describing Pu(IV)/Pu(V) sorption to aluminol and silanol groups were developed from the silica and gibbsite sorption experiments and applied to the montmorillonite dataset. The model provided an acceptable fit to the montmorillonite sorption data for Pu(V). In order to accurately predict Pu(IV) sorption to montmorillonite, the model required inclusion of ion exchange. The objective of this work is to measure the sorption of Pu(IV) and Pu(V) to silica, gibbsite, and smectite (montmorillonite). Aluminosilicate minerals are ubiquitous at the Nevada National Security Site and improving our understanding of Pu sorption to aluminosilicates (smectite clays in particular) is essential to the accurate prediction of Pu transport rates. These data will improve the mechanistic approach for modeling the hydrologic source term (HST) and provide sorption Kd parameters for use in CAU models. In both alluvium and tuff, aluminosilicates have been found to play a dominant role in the radionuclide retardation because their abundance is typically more than an order of magnitude greater than other potential sorbing minerals such as iron and manganese oxides (e.g. Vaniman et al., 1996). The sorption database used in recent HST models (Carle et al., 2006) and upscaled for use in CAU models (Stoller-Navarro, 2008) includes surface complexation constants for U, Am, Eu, Np and Pu (Zavarin and Bruton, 2004). Generally, between 15 to 30 datasets were used to develop the constants for each radionuclide. However, the constants that describe Pu sorption to aluminosilicates were developed using only 10 datasets, most of which did not specify the oxidation state of Pu in the experiment. Without knowledge or control of the Pu oxidation state, a high degree of uncertainty is introduced into the model. The existing Pu surface complexation model (e.g. Zavarin and Bruton, 2004) drastically underestimates Pu sorption and, thus, will overestimate Pu migration rates (Turner, 1995). Recent HST simulations at Cambric (Carle et al., 2006) suggest that the existing surface complexation model may underpredict Pu K{sub d}s by as much as 3 orders of magnitude. In order to improve HST and CAU-scale transport models (and, as a result, reduce the conservative nature Pu migration estimates), sorption experiments were performed over a range of solution conditions that brackets the groundwater chemistry of the Nevada National Security Site. The aluminosilicates examined were gibbsite, silica, and montmorillonite
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Modeling of Groundwater Flow and Radionuclide Transport at the Climax Mine sub-CAU, Nevada Test Site
The Yucca Flat-Climax Mine Corrective Action Unit (CAU) on the Nevada Test Site comprises 747 underground nuclear detonations, all but three of which were conducted in alluvial, volcanic, and carbonate rocks in Yucca Flat. The remaining three tests were conducted in the very different hydrogeologic setting of the Climax Mine granite stock located in Area 15 at the northern end of Yucca Flat. As part of the Corrective Action Investigation (CAI) for the Yucca Flat-Climax Mine CAU, models of groundwater flow and radionuclide transport will be developed for Yucca Flat. However, two aspects of these CAU-scale models require focused modeling at the northern end of Yucca Flat beyond the capability of these large models. First, boundary conditions and boundary flows along the northern reaches of the Yucca Flat-Climax Mine CAU require evaluation to a higher level of detail than the CAU-scale Yucca Flat model can efficiently provide. Second, radionuclide fluxes from the Climax tests require analysis of flow and transport in fractured granite, a unique hydrologic environment as compared to Yucca Flat proper. This report describes the Climax Mine sub-CAU modeling studies conducted to address these issues, with the results providing a direct feed into the CAI for the Yucca Flat-Climax Mine CAU. Three underground nuclear detonations were conducted for weapons effects testing in the Climax stock between 1962 and 1966: Hard Hat, Pile Driver, and Tiny Tot. Though there is uncertainty regarding the position of the water table in the stock, it is likely that all three tests were conducted in the unsaturated zone. In the early 1980s, the Spent Fuel Test-Climax (SFT-C) was constructed to evaluate the feasibility of retrievable, deep geologic storage of commercial nuclear reactor wastes. Detailed mapping of fractures and faults carried out for the SFT-C studies greatly expanded earlier data sets collected in association with the nuclear tests and provided invaluable information for subsequent modeling studies at Climax. The objectives of the Climax Mine sub-CAU work are to (1) provide simulated heads and groundwater flows for the northern boundaries of the Yucca Flat-Climax Mine CAU model, while incorporating alternative conceptualizations of the hydrogeologic system with their associated uncertainty, and (2) provide radionuclide fluxes from the three tests in the Climax stock using modeling techniques that account for groundwater flow in fractured granite. Meeting these two objectives required two different model scales. The northern boundary groundwater fluxes were addressed using the Death Valley Regional Flow System (DVRFS) model (Belcher, 2004) developed by the U.S. Geological Survey as a modeling framework, with refined hydrostratigraphy in a zone north of Yucca Flat and including Climax stock. Radionuclide transport was simulated using a separate model confined to the granite stock itself, but linked to regional groundwater flow through boundary conditions and calibration targets
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Radionuclide Reaction Chemistry as a Function of Temperature at the Cheshire Site
The goals of this task were to evaluate the availability of published temperature-dependent thermodynamic data for radionuclides and sorbing minerals and to evaluate the applicability of published estimation methods for temperature-dependent aqueous complexation, radionuclide mineral precipitation, and sorption. This task fills a gap in the hydrologic source term (HST) modeling approach, which, with few exceptions, has neglected the effects of temperature on radionuclide aqueous complexation, using 25 C complexation data for all temperatures without evaluating the consequences of this assumption. In this task, we have compiled thermodynamic data available in the literature and evaluated the options and benefits of applying temperature-dependent radionuclide speciation to future HST modeling. We use the recent experience of HST modeling at Cheshire (Pawloski et al., 2001) to focus our evaluation. Our literature search revealed that few thermodynamic data or extrapolation methods could be used to define the temperature-dependent speciation of key HST radionuclides Np, Pu, Am, and U, particularly for the higher valence-state (e.g., 5+ and 6+), the oxidation states most pertinent to NTS groundwater conditions at Cheshire. This suggests that using 25 C data for all temperatures may be the best modeling approach currently available. We tested established estimation techniques such as the Criss-Cobble method and other correlation algorithms to calculate thermodynamic parameters needed to extrapolate aqueous complexation data to higher temperatures. For some reactions, the isocoulombic method does allow calculation of free energy data and equilibrium values at higher temperatures. Limitations in algorithms and input data for pentavalent and hexavalent cations prevent extending temperature ranges for reactions involving radionuclides in these oxidation states and their complexes. In addition, for many of the radionuclides of interest, carbonate complexes appear to be the dominant complexes formed in NTS groundwaters, and data for these types of complexes are lacking for radionuclides as well as analog species. For the few species where enough data are available, the effect of temperature on radionuclide aqueous complexation has been calculated. These calculations allow partial estimation of the potential error that may be involved in ignoring speciation changes as a function of temperature, as was done in the Cheshire HST model (Pawloski et al., 2001). In some cases, differences between the most recent 25 C data available in the literature and data used in Pawloski et al. (2001) were more significant than calculated speciation changes as a function of temperature. To incorporate radionuclide speciation as a function of temperature, a robust set of temperature-dependent reaction constants is necessary. Based on our literature search and the few reactions that could be extrapolated to higher temperatures, the change in dominant complexes with temperature cannot be adequately addressed at this time. However, the effect of temperature on speciation can be qualitatively examined. In general, the log K values for radionuclide complexation reactions considered here increase with increasing temperature, suggesting that increasing temperature may enhance radionuclide aqueous complexation. However, complexation reactions often involve H{sup +} and reactant species such as carbonate which exhibit their own temperature-dependent speciation. Thus, any change in the value of a radionuclide complexation log K may be offset or enhanced by temperature effects on pH and carbonate speciation. In addition, sorption processes that involve surface complexation change with increasing temperature, and these reactions may enhance or negate the mobility effects of any increase in aqueous complexation with temperature. While increasing temperature may increase complexation, it also may reduce or increase ligand concentrations through shifts in speciation. Similarly, higher temperatures may favor or reduce sorption and/or co-precipitation in mineral phases. Consequently, the net effect on radionuclide mobility of increasing temperature depends on the effects of temperature on a number of geochemical processes. Thus, it is even difficult to make qualitative assumptions about the direction much less the magnitude of temperature effects on radionuclide mobility. Until sufficient data become available in the literature to precisely capture the effects of temperature on radionuclide complexation, it appears unwarranted to invest in complex estimation techniques based on extrapolations from available data
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