Aging effects on Cesium-137 (137Cs) sorption and transport in association with clay colloids.

Migration of radionuclides via colloid-facilitated transport is an important component of nuclear repository performance models. 137Cs sorption to bentonite colloids follows multi-site behavior, with sorption to weak sites being a rapid process and sorption to strong sites having slow kinetics. Experiments in this study targeted desorption of 137Cs from strong sites on the colloids by placing the 137Cs-bearing colloids in contact with a strongly-sorbing zeolite material that competes with the colloids for 137Cs sorption. Batch and column experiments were conducted to examine the effects of aging (i.e., increased contact time between 137Cs and colloids) on colloid-facilitated transport of 137Cs through crushed analcime columns. A larger proportion of 137Cs-bearing colloids eluted through a series of columns when the colloids were aged for 1200 days prior to injection in comparison to unaged colloids. Aging the colloids increased the partitioning of 137Cs to the colloids by nearly 20% after 1200 h. Slow desorption (0.27 hr-1) from the strong sites resulted in an increase of the Cs fraction bound to the strong sites from 0.365 to 0.87 by the second column injection, resulting in increased colloid-facilitated transport of Cs through strongly-sorbing zeolites from 0 in the second unaged column to 10% in the second aged column.

Field experiments of surface water to groundwater recharge to characterize the mobility of uranium and vanadium at a former mill tailing site.

Characterizing the mobility of uranium and vanadium in groundwater with a hydraulic connection to surface water is important to inform the best management practices of former mill tailing sites. In this study, the recharge of river water to the unsaturated and saturated zones of a uranium-contaminated alluvial aquifer was simulated in a series of forced-gradient single- and multi-well injection-extraction tests. The injection fluid (river water) was traced with natural and artificial tracers that included halides, fluorobenzoates, lithium, and naphthalene sulfonate to characterize the potential mass transport mechanisms of uranium and vanadium. The extraction fluid (river water/groundwater mixture) was analyzed for the tracers, uranium, and vanadium. The results from the tracers indicated that matrix diffusion was likely negligible over the spatiotemporal scales of the tests as evident by nearly identical breakthrough curves of the halides and fluorobenzoates. In contrast, the breakthrough curves of lithium and naphthalene sulfonate indicated that sorption by cation exchange and sorption to organic matter, respectively, were potential mass transport mechanisms of uranium and vanadium. Uranium was mobilized in the saturated zone containing gypsum (gypsum-rich zone), the vadose zone (vadose-rich zone), and the saturated zone containing organic carbon (organic-rich zone) whereas vanadium was mobilized only in the saturated gypsum-rich zone. The mechanisms responsible for the mobilization of uranium and vanadium were likely dissolution of uranium- and vanadium-bearing minerals and/or desorption from the gypsum-rich zone, flushing of uranium from the vadose-rich zone, and desorption of uranium from the organic-rich zone due to the natural contrast in the geochemistry between the river water and groundwater. The experimental design of this study was unique in that it employed the use of multiple natural and artificial tracers coupled with a direct injection of native river water to groundwater. These results demonstrated that natural recharge and flooding events at former mill tailing sites can mobilize uranium, and possibly vanadium, and contribute to persistent levels of groundwater contamination.

Uranium Natural Attenuation Downgradient of an in Situ Recovery Mine Inferred from a Cross-Hole Field Test.

A field test was conducted at a uranium in situ recovery (solution mining) site to evaluate postmining uranium natural attenuation downgradient of an ore zone. Approximately 1 million liters of water from a previously mined ore zone was injected into an unmined ore zone that served as a proxy for a downgradient aquifer, while a well located approximately 23 m away was pumped. After 1 year of pumping, only about 39% of the injected U(VI) was recovered, whereas essentially 100% of coinjected chloride was recovered. A geochemical/transport model was used to simultaneously match the chloride and uranium concentrations at the pumping well while also qualitatively matching aqueous 238U/235U ratios, which reflect uranium removal from solution by reduction. It was concluded that ∼50% of the injected U(VI) was reduced to U(IV), although the reduction capacity in the flow pathways between the injection and production wells was estimated to be nearly exhausted by the end of the test. Estimating the reduction capacity of the downgradient aquifer can inform restoration strategy and offer a useful metric for regulatory decisions concerning the adequacy of restoration. U(VI) reduction should be effectively irreversible in these anoxic environments, which differ greatly from shallow oxic environments where U(IV) is readily reoxidized.

Uncertainty and variability in laboratory derived sorption parameters of sediments from a uranium in situ recovery site.

This research assesses the ability of a GC SCM to simulate uranium transport under variable geochemical conditions typically encountered at uranium in-situ recovery (ISR) sites. Sediment was taken from a monitoring well at the SRH site at depths 192 and 193 m below ground and characterized by XRD, XRF, TOC, and BET. Duplicate column studies on the different sediment depths, were flushed with synthesized restoration waters at two different alkalinities (160 mg/l CaCO3 and 360 mg/l CaCO3) to study the effect of alkalinity on uranium mobility. Uranium breakthrough occurred 25% - 30% earlier in columns with 360 mg/l CaCO3 over columns fed with 160 mg/l CaCO3 influent water. A parameter estimation program (PEST) was coupled to PHREEQC to derive site densities from experimental data. Significant parameter fittings were produced for all models, demonstrating that the GC SCM approach can model the impact of carbonate on uranium in flow systems. Derived site densities for the two sediment depths were between 141 and 178 µmol-sites/kg-soil, demonstrating similar sorption capacities despite heterogeneity in sediment mineralogy. Model sensitivity to alkalinity and pH was shown to be moderate compared to fitted site densities, when calcite saturation was allowed to equilibrate. Calcite kinetics emerged as a potential source of error when fitting parameters in flow conditions. Fitted results were compared to data from previous batch and column studies completed on sediments from the Smith-Ranch Highland (SRH) site, to assess variability in derived parameters. Parameters from batch experiments were lower by a factor of 1.1 to 3.4 compared to column studies completed on the same sediments. The difference was attributed to errors in solid-solution ratios and the impact of calcite dissolution in batch experiments. Column studies conducted at two different laboratories showed almost an order of magnitude difference in fitted site densities suggesting that experimental methodology may play a bigger role in column sorption behavior than actual sediment heterogeneity. Our results demonstrate the necessity for ISR sites to remove residual pCO2 and equilibrate restoration water with background geochemistry to reduce uranium mobility. In addition, the observed variability between fitted parameters on the same sediments highlights the need to provide standardized guidelines and methodology for regulators and industry when the GC SCM approach is used for ISR risk assessments.

Comparison of experimental methods for estimating matrix diffusion coefficients for contaminant transport modeling.

Diffusion cell and diffusion wafer experiments were conducted to compare methods for estimating effective matrix diffusion coefficients in rock core samples from Pahute Mesa at the Nevada Nuclear Security Site (NNSS). A diffusion wafer method, in which a solute diffuses out of a rock matrix that is pre-saturated with water containing the solute, is presented as a simpler alternative to the traditional through-diffusion (diffusion cell) method. Both methods yielded estimates of effective matrix diffusion coefficients that were within the range of values previously reported for NNSS volcanic rocks. The difference between the estimates of the two methods ranged from 14 to 30%, and there was no systematic high or low bias of one method relative to the other. From a transport modeling perspective, these differences are relatively minor when one considers that other variables (e.g., fracture apertures, fracture spacings) influence matrix diffusion to a greater degree and tend to have greater uncertainty than effective matrix diffusion coefficients. For the same relative random errors in concentration measurements, the diffusion cell method yields effective matrix diffusion coefficient estimates that have less uncertainty than the wafer method. However, the wafer method is easier and less costly to implement and yields estimates more quickly, thus allowing a greater number of samples to be analyzed for the same cost and time. Given the relatively good agreement between the methods, and the lack of any apparent bias between the methods, the diffusion wafer method appears to offer advantages over the diffusion cell method if better statistical representation of a given set of rock samples is desired.

Evaluation of multiple tracer methods to estimate low groundwater flow velocities.

Four different tracer methods were used to estimate groundwater flow velocity at a multiple-well site in the saturated alluvium south of Yucca Mountain, Nevada: (1) two single-well tracer tests with different rest or "shut-in" periods, (2) a cross-hole tracer test with an extended flow interruption, (3) a comparison of two tracer decay curves in an injection borehole with and without pumping of a downgradient well, and (4) a natural-gradient tracer test. Such tracer methods are potentially very useful for estimating groundwater velocities when hydraulic gradients are flat (and hence uncertain) and also when water level and hydraulic conductivity data are sparse, both of which were the case at this test location. The purpose of the study was to evaluate the first three methods for their ability to provide reasonable estimates of relatively low groundwater flow velocities in such low-hydraulic-gradient environments. The natural-gradient method is generally considered to be the most robust and direct method, so it was used to provide a "ground truth" velocity estimate. However, this method usually requires several wells, so it is often not practical in systems with large depths to groundwater and correspondingly high well installation costs. The fact that a successful natural gradient test was conducted at the test location offered a unique opportunity to compare the flow velocity estimates obtained by the more easily deployed and lower risk methods with the ground-truth natural-gradient method. The groundwater flow velocity estimates from the four methods agreed very well with each other, suggesting that the first three methods all provided reasonably good estimates of groundwater flow velocity at the site. The advantages and disadvantages of the different methods, as well as some of the uncertainties associated with them are discussed.

Se Isotopes as Groundwater Redox Indicators: Detecting Natural Attenuation of Se at an in Situ Recovery U Mine.

One of the major ecological concerns associated with the in situ recovery (ISR) of uranium (U) is the environmental release of soluble, toxic selenium (Se) oxyanions generated by mining. Post-mining natural attenuation by the residual reductants in the ore body and reduced down-gradient sediments should mitigate the risk of Se contamination in groundwater. In this work, we investigate the Se concentrations and Se isotope systematics of groundwater and of U ore bearing sediments from an ISR site at Rosita, TX, USA. Our results show that selenate (Se(VI)) is the dominant Se species in Rosita groundwater, and while several up-gradient wells have elevated Se(VI), the majority of the ore zone and down-gradient wells have little or no Se oxyanions. In addition, the δ82SeVI of Rosita groundwater is generally elevated relative to the U ore up to +6.14‰, with the most enriched values observed in the ore-zone wells. Increasing δ82Se with decreasing Se(VI) conforms to a Rayleigh type distillation model with an ε of -2.25‰ ± 0.61‰, suggesting natural Se(VI) reduction occurring along the hydraulic gradient at the Rosita ISR site. Furthermore, our results show that Se isotopes are excellent sensors for detecting and monitoring post-mining natural attenuation of Se oxyanions at ISR sites.

Reactive transport of uranium in fractured crystalline rock: Upscaling in time and distance.

Batch adsorption and breakthrough column experiments were conducted to evaluate uranium transport through altered material that fills fractures in a granite rock system at the Grimsel Test Site in Switzerland at pH 6.9 and 7.9. The role of adsorption and desorption kinetics was evaluated with reactive transport modeling by comparing one-, two-, and three-site models. Emphasis was placed on describing long desorption tails that are important for upscaling in time and distance. The effect of increasing pH in injection solutions was also evaluated. For pH 6.9, a three-site model with forward rate constants between 0.07 and 0.8 ml g(-1) h(-1), reverse rate constants between 0.001 and 0.06 h(-1), and site densities of 1.3, 0.104, and 0.026 µmol g(-1) for 'weak/fast', 'strong/slow', and 'very strong/very slow' sites provided the best fits. For pH 7.9, a three-site model with forward rate constants between 0.05 and 0.8 mL g(-1) h(-1), reverse rate constants between 0.001 and 0.6 h(-1), and site densities of 1.3, 0.039, and 0.013 µmol g(-1) for a 'weak/fast', 'strong/slow', and 'very strong/very slow' sites provided the best fits. Column retardation coefficients (Rd) were 80 for pH 6.9 and 10.3 for pH 7.9. Model parameters determined from the batch and column experiments were used in 50 year large-scale simulations for continuous and pulse injections and indicated that a three-site model is necessary at pH 6.9, although a Kd-type equilibrium partition model with one-site was adequate for large scale predictions at pH 7.9. Batch experiments were useful for predicting early breakthrough times in the columns while column experiments helped differentiate the relative importance of sorption sites and desorption rate constants on transport.

Genome Sequence of a Chromium-Reducing Strain, Bacillus cereus S612.

We report here the genome sequence of an effective chromium-reducing bacterium, Bacillus cereus strain S612. The size of the draft genome sequence is approximately 5.4 Mb, with a G+C content of 35%, and it is predicted to contain 5,450 protein-coding genes.

Isotopic and Geochemical Tracers for U(VI) Reduction and U Mobility at an in Situ Recovery U Mine.

In situ recovery (ISR) uranium (U) mining mobilizes U in its oxidized hexavalent form (U(VI)) by oxidative dissolution of U from the roll-front U deposits. Postmining natural attenuation of residual U(VI) at ISR mines is a potential remediation strategy. Detection and monitoring of naturally occurring reducing subsurface environments are important for successful implementation of this remediation scheme. We used the isotopic tracers (238)U/(235)U (δ(238)U), (234)U/(238)U activity ratio, and (34)S/(32)S (δ(34)S), and geochemical measurements of U ore and groundwater collected from 32 wells located within, upgradient, and downgradient of a roll-front U deposit to detect U(VI) reduction and U mobility at an ISR mining site at Rosita, TX, USA. The δ(238)U in Rosita groundwater varies from +0.61‰ to -2.49‰, with a trend toward lower δ(238)U in downgradient wells. The concurrent decrease in U(VI) concentration and δ(238)U with an ε of 0.48‰ ± 0.08‰ is indicative of naturally occurring reducing environments conducive to U(VI) reduction. Additionally, characteristic (234)U/(238)U activity ratio and δ(34)S values may also be used to trace the mobility of the ore zone groundwater after mining has ended. These results support the use of U isotope-based detection of natural attenuation of U(VI) at Rosita and other similar ISR mining sites.

Matrix diffusion coefficients in volcanic rocks at the Nevada test site: influence of matrix porosity, matrix permeability, and fracture coating minerals.

Diffusion cell experiments were conducted to measure nonsorbing solute matrix diffusion coefficients in forty-seven different volcanic rock matrix samples from eight different locations (with multiple depth intervals represented at several locations) at the Nevada Test Site. The solutes used in the experiments included bromide, iodide, pentafluorobenzoate (PFBA), and tritiated water ((3)HHO). The porosity and saturated permeability of most of the diffusion cell samples were measured to evaluate the correlation of these two variables with tracer matrix diffusion coefficients divided by the free-water diffusion coefficient (D(m)/D*). To investigate the influence of fracture coating minerals on matrix diffusion, ten of the diffusion cells represented paired samples from the same depth interval in which one sample contained a fracture surface with mineral coatings and the other sample consisted of only pure matrix. The log of (D(m)/D*) was found to be positively correlated with both the matrix porosity and the log of matrix permeability. A multiple linear regression analysis indicated that both parameters contributed significantly to the regression at the 95% confidence level. However, the log of the matrix diffusion coefficient was more highly-correlated with the log of matrix permeability than with matrix porosity, which suggests that matrix diffusion coefficients, like matrix permeabilities, have a greater dependence on the interconnectedness of matrix porosity than on the matrix porosity itself. The regression equation for the volcanic rocks was found to provide satisfactory predictions of log(D(m)/D*) for other types of rocks with similar ranges of matrix porosity and permeability as the volcanic rocks, but it did a poorer job predicting log(D(m)/D*) for rocks with lower porosities and/or permeabilities. The presence of mineral coatings on fracture walls did not appear to have a significant effect on matrix diffusion in the ten paired diffusion cell experiments.

Testing and parameterizing a conceptual solute transport model in saturated fractured tuff using sorbing and nonsorbing tracers in cross-hole tracer tests.

Two cross-hole tracer tests involving the simultaneous injection of two nonsorbing solute tracers with different diffusion coefficients (bromide and pentafluorobenzoate) and one weakly sorbing solute tracer (lithium ion) were conducted in two different intervals at the C-wells complex near the site of a potential high-level nuclear waste repository at Yucca Mountain, NV. The tests were conducted to (1) test a conceptual radionuclide transport model for saturated, fractured tuffs near Yucca Mountain and (2) obtain transport parameter estimates for predictive modeling of radionuclide transport. The differences between the responses of the two nonsorbing tracers and the sorbing tracer (when normalized to injection masses) were consistent with a dual-porosity transport system in which matrix diffusion was occurring. The concentration attenuation of the sorbing tracer relative to the nonsorbing tracers suggested that diffusion occurred primarily into matrix pores, not simply into stagnant water within the fractures. The K(d) values deduced from the lithium responses were generally larger than K(d) values measured in laboratory batch sorption tests using crushed C-wells cores. This result supports the use of laboratory-derived K(d) values for predicting sorbing species transport at the site, as the laboratory K(d) values would result in underprediction of sorption and hence conservative transport predictions. The tracer tests also provided estimates of effective flow porosity and longitudinal dispersivity at the site. The tests clearly demonstrated the advantages of using multiple tracers of different physical and chemical characteristics to distinguish between alternative conceptual transport models and to obtain transport parameter estimates that are better constrained than can be obtained using only a single tracer or using multiple nonsorbing tracers without a sorbing tracer.

Transport of a reactive tracer in saturated alluvium described using a three-component cation-exchange model.

A weakly sorbing cation, lithium, will be used as a reactive tracer in upcoming field tracer tests in the saturated alluvium south of Yucca Mountain, Nevada. One objective of the field tests is to determine how well field-scale reactive transport can be predicted using transport parameters derived from laboratory experiments. This paper describes several laboratory lithium batch sorption and column transport experiments that were conducted using ground water and alluvium obtained from the site of the planned field tests. In the batch experiments, isotherms were determined over 2.5 orders of magnitude of lithium concentrations, corresponding to the range expected in the field tests. In addition to measuring equilibrium lithium concentrations, concentrations of other cations, namely Na(+), K(+), and Ca(2+), were measured in the batch tests to determine Li(+)-exchangeable equilibria. This information was used in conjunction with alluvium cation exchange capacity measurements to parameterize a three-component cation-exchange model (EQUIL) that describes lithium sorption in the alluvium system. This model was then applied to interpret the transport behavior of lithium ion in saturated alluvium column tests conducted at three different lithium bromide injection concentrations. The concentrations were selected such that lithium ion either dominated, accounted for a little over half, or accounted for only a small fraction of the total cation equivalents in the injection solution. Although tracer breakthrough curves differed significantly under each of these conditions, with highly asymmetric responses occurring at the highest injection concentrations, the three-component cation-exchange model reproduced the observed transport behavior of lithium and the other cations in each case with a similar set of model parameters. In contrast, a linear K(d)-type sorption model could only match the lithium responses at the lowest injection concentration. The three-component model will be used to interpret the field tests, with the expectation that it will help refine estimates of effective flow porosity, particularly if the lithium response curves are asymmetric.

Automated video microscopic imaging and data acquisition system for colloid deposition measurements.

An optical video microscopic system and image processing and data extraction and manipulation routines are developed for in situ detailed quantification of the deposition of colloids onto an arbitrary surface and determining their concentration distribution across the bulk suspension. The system produces a relatively large field of view (approximately 330 x 245 microm) and utilizes dark-field light microscopy to visualize colloids as small as approximately 0.3 microm in diameter at the surface and in the bulk suspension with a sufficient resolution (approximately 0.5 microm). On real-time basis, the routines automate various tasks from image capturing and processing to data manipulation, extraction, and display. The extracted data include: (i) surface concentration and flux of deposited, attached, and detached colloids, (ii) surface concentration and flux of arriving and departing colloids, (iii) distribution of colloids in the bulk suspension in the direction perpendicular to the deposition surface, and (iv) spatial and temporal distributions of deposited colloids. This article provides detailed description of the system and its image processing and data extraction and manipulation routines. Representative results of the deposition of 0.3-microm-diameter polystyrene colloids onto a glass surface, from a flowing suspension in a 0.02-cm-aperture parallel-plate channel, are presented and discussed.

On visualization of sub-micron particles with dark-field light microscopy.

Dark-field light microscopy is widely employed to visualize colloidal particles much smaller than the light wavelength used. In the captured images, the colloidal particles appear, against a dark background, as bright "specks" much larger than the geometrical size of the particles. To verify whether the "specks" are for individual particles or clusters of particles, experiments are performed which used low bulk concentrations of five suspensions of monodispersed particles (approximately 0.3 microm in diameter) and a dark-field video microscopic system with an optical resolution of approximately 0.5 microm to count the particles after they all have deposited onto the inner surfaces of a parallel-plate glass channel. The average size and the size distribution of the particles are also determined at the end of each experiment. The results confirmed that the visualized "specks" are for individual particles. The measured and prepared particle bulk concentrations in the five experiments closely matched, to within +/-5%, and the measured average size of the particles and their size distribution at the end of the five experiments were in agreement with the known values.