In situ mobilization of colloids and transport of cesium in Hanford sediments

Radioactive waste, accumulated during Pu production, has leaked into the subsurface from underground storage tanks at the U.S. Department of Energy's Hanford site. The leaking solutions contained 137Cs and were of high ionic strength. Such a tank leak was simulated experimentally in steady-state flow experiments with packed Hanford sediments. The initial leak was simulated by a 1 M NaNO3 solution, followed by a decrease of ionic strength to 1 mM NaNO3. Cesium breakthrough curves were determined in both 1 M and 1 mM NaNO3 background. Colloidal particles were mobilized during the change of ionic strength. Mobilized colloids consisted mainly of quartz, mica, illite, kaolinite, and chlorite. Electrophoretic mobilities of colloids in the eluent solution were -3(microm/s)(V/cm) and increased to less negative values during later stages of mobilization. Mobilized colloids carried a fraction of the cesium along. While transport of cesium in 1 M NaNO3 background was much faster than in 1 mM NaNO3, cesium attached to colloids moved almost unretarded through the sediments. Cesium attached to mobilized colloids was likely associated with high affinity sorption sites on micas and illites.     

Colloid-facilitated Cs transport through water-saturated Hanford sediment and Ottawa sand

In this study, a series of saturated column experiments were conducted to investigate effects of colloids on Cs transport in two types of porous media (Hanford sediment characteristic of 2:1 clay minerals and silica Ottawa sand). The colloids used were obtained by reacting Hanford sediment with simulated tank waste solutions. Because of the highly nonlinear nature of Cs sorption found in batch experiments, we used two different concentrations of Cs (7.5 x 10(-5) M and 1.4 x 10(-8) M) for the transport experiments. The presence of colloids facilitated the transport of Cs through both Hanford sediment and Ottawa sand via association of Cs with mobile colloidal particles. Due to the nonlinearity of the Cs sorption, the colloid-facilitated Cs transportwas more pronounced atthe low Cs concentration (1.4 x 10(-8) M) than at the high concentration (7.5 x 10(-5) M) when expressed relative to the inflow Cs concentration. In the absence of colloids, no Cs moved through the 10-cm long columns during the experiment within about 20 pore volumes, exceptfor the high Cs concentration in the Ottawa sand where a complete Cs breakthrough was obtained. Also, it was found that colloid-associated Cs could be partially stripped off from colloids during the transport. The stripping effect was controlled by both Cs concentration and sorption capacity of the transport matrix.     

Strontium and cesium release mechanisms during unsaturated flow through waste-weathered Hanford sediments

Leaching behavior of Sr and Cs in the vadose zone of Hanford site (Washington) was studied with laboratory-weathered sediments mimicking realistic conditions beneath the leaking radioactive waste storage tanks. Unsaturated column leaching experiments were conducted using background Hanford pore water focused on first 200 pore volumes. The weathered sediments were prepared by 6 months reaction with a synthetic Hanford tank waste leachate containing Sr and Cs (10(-5) and 10(-3) molal representative of LO- and HI-sediment, respectively) as surrogates for (90)Sr and (137)Cs. The mineral composition of the weathered sediments showed that zeolite (chabazite-type) and feldspathoid (sodalite-type) were the major byproducts but different contents depending on the weathering conditions. Reactive transport modeling indicated that Cs leaching was controlled by ion-exchange, while Sr release was affected primarily by dissolution of the secondary minerals. The later release of K, Al, and Si from the HI-column indicated the additional dissolution of a more crystalline mineral (cancrinite-type). A two-site ion-exchange model successfully simulated the Cs release from the LO-column. However, a three-site ion-exchange model was needed for the HI-column. The study implied that the weathering conditions greatly impact the speciation of the secondary minerals and leaching behavior of sequestrated Sr and Cs.     

Colloid stability in vadose zone Hanford sediments

We experimentally determined colloid stability of natural colloids extracted from vadose zone sediments from the U.S. Department of Energy's Hanford Reservation. We also used reference minerals, kaolinite, montmorillonite, and silica,for comparative purposes. Colloid stability was assessed with two different methods: the batch turbidity method and dynamic light scattering. Critical coagulation concentrations (CCCs) were determined for pure Na and pure Ca electrolyte solutions, as well for mimicked Hanford vadose zone pore waters with varying sodium adsorption ratios (SARs). Critical coagulation concentrations obtained from the batch turbidity method were sensitive to initial colloid mass concentrations, settling time, and CCC criteria. The lower the initial colloid concentration and the shorter the settling times were, the larger was the CCC. The CCCs determined from the dynamic light scattering, where diluted colloidal suspensions are used, were not dependent on settling time and arbitrary CCC criteria, so dynamic light scattering is therefore the preferred method to determine colloid stability. The CCC values determined from dynamic light scattering ranged from 90 to 200 mmol/L for Na systems and 1.7 to 3.8 mmol/L for Ca systems. The stability of natural colloids was intermediate between that of pure kaolinite and montmorillonite. The results indicate that colloids in the Hanford vadose zone form stable suspensions, i.e., are in the slow aggregation regime. Nonetheless, due to the long travel times in the vadose zone, nearly all colloids will aggregate and be removed from the water column before reaching groundwater levels.     

Colloid formation in Hanford sediments reacted with simulated tank waste

Solutions of high pH, ionic strength, and aluminum concentration have leaked into the subsurface from underground waste storage tanks atthe Hanford Reservation in Washington State. Here, we test the hypothesis that these waste solutions alter and dissolve the native minerals present in the sediments and that colloidal (diameter < 2 microm) feldspathoids form. We reacted Hanford sediments with simulated solutions representative of Hanford waste tanks. The solutions consisted of 1.4 or 2.8 mol/kg NaOH, 0.125 or 0.25 mol/kg NaAlO4, and 3.7 mol/kg NaNO3 and were contacted with the sediments for a period of 25 or 40 days at 50 degrees C. The colloidal size fraction was separated from the sediments and characterized in terms of mineralogy, morphology, chemical composition, and electrophoretic mobility. Upon reaction with tank waste solutions, native minerals released Si and other elements into the solution phase. This Si precipitated with the Al present in the waste solutions to form secondary minerals, identified as the feldspathoids cancrinite and sodalite. The solution phase was modeled with the chemical equilibrium model GMIN for solution speciation and saturation indices with respect to sodalite and cancrinite. The amount of colloidal material in the sediments increased upon reaction with waste solutions. At the natural pH found in Hanford sediments (pH 8) the newly formed minerals are negatively charged, similar to the unreacted colloidal material present in the sediments. The formation of colloidal material in Hanford sediments upon reaction with tank waste solutions is an important aspect to consider in the characterization of Hanford tank leaks and may affect the fate of hazardous radionuclides present in the tank waste.     

Changes in uranium speciation through a depth sequence of contaminated Hanford sediments

The disposal of basic sodium aluminate and acidic U(VI)-Cu(ll) wastes in the now-dry North and South 300 A Process Ponds atthe Hanford site resulted in a groundwater plume of U(VI). To gain insight into the geochemical processes that occurred during waste disposal and those affecting the current and future fate and transport of this uranium plume, the solid-phase speciation of uranium in a depth sequence of sediments from the base of the North Process Pond through the vadose zone to groundwater was investigated using standard chemical and mineralogical analyses, electron and X-ray microprobe measurements, and X-ray absorption fine structure spectroscopy. Near-surface sediments contained uranium coprecipitated with calcite, which formed due to overneutralization of the waste ponds with base (NaOH). At intermediate depths in the vadose zone, metatorbernite [Cu(UO2PO4)2 x 8H2O] precipitated, likely during pond operations. Uranium occurred predominantly sorbed onto phyllosilicates in the deeper vadose zone and groundwater; sorbed uranium was also an important component at intermediate depths. Since the calcite-bearing pond sediments have been removed in remediation efforts, uranium fate and transport will be controlled primarily by desorption of the sorbed uranium and dissolution of metatorbernite.     

Transport of methane and noble gases during gas push-pull tests in variably saturated porous media

The gas push-pull test (GPPT) is a single-well gas-tracer method to quantify in situ rates of CH4 oxidation in soils. To improve the design and interpretation of GPPT field experiments, gas component transport during GPPTs was examined in abiotic porous media over a range of water saturations (0.0 < or = Sw < or = 0.61). A series of GPPTs using He, Ne, and Ar as tracers for CH4 were performed at two injection/extraction gas flow rates (approximately 200 and approximately 700 mL min(-1)) in a laboratory tank. Extraction phase breakthrough curves and mass recovery curves of the gaseous components became more similar at higher Sw as water in the pore space restricted diffusive gas-phase transport. Diffusional fractionation of the stable carbon isotopes of CH4 during the extraction period of GPPTs also decreased with increasing Sw (particularly when Sw > 0.42). Gas-component transport during GPPTs was numerically simulated using estimated hydraulic parameters for the porous media and no fitting of data for the GPPTs. Numerical simulations accurately predicted the relative decline of the gaseous components in the breakthrough curves, but slightly overestimated recoveries at low Sw (< or = 0.35) and underestimated recoveries at high Sw (> or = 0.49). Comparison of numerical simulations considering and not considering air-water partitioning indicated that removal of gaseous components through dissolution in pore water was not significant during GPPTs, even at Sw = 0.61. These data indicate that Ar is a good tracer for CH4 physical transport over the full range of Sw studied, whereas, at Sw > 0.61, any of the tracers could be used. Greater mass recovery at higher Sw raises the possibility to reduce gas flow rates, thereby extending GPPT times in environments such as tundra soils where low activity due to low temperatures may require longer test times to establish a quantifiable difference between reactant and tracer breakthrough curves.     

Distribution and retention of 137Cs in sediments at the Hanford Site, Washington

137Cesium and other contaminants have leaked from single-shell storage tanks (SSTs) into coarse-textured, relatively unweathered unconsolidated sediments. Contaminated sediments were retrieved from beneath a leaky SST to investigate the distribution of adsorbed 137Cs+ across different sediment size fractions. All fractions contained mica (biotite, muscovite, vermiculatized biotite), quartz, and plagioclase along with smectite and kaolinite in the clay-size fraction. A phosphor-plate autoradiograph method was used to identify particular sediment particles responsible for retaining 137Cs+. The Cs-bearing particles were found to be individual mica flakes or agglomerated smectite, mica, quartz, and plagioclase. Of these, only the micaceous component was capable of sorbing Cs+ strongly. Sorbed 137Cs+ could not be significantly removed from sediments by leaching with dithionite citrate buffer or KOH, but a fraction of the sorbed 137Cs+ (5-22%) was desorbable with solutions containing an excess of Rb+. The small amount of 137Cs+ that might be mobilized by migrating fluids in the future would likely sorb to nearby micaceous clasts in downgradient sediments.     

Mobility of cesium through the Callovo-Oxfordian claystones under partially saturated conditions

The diffusion of cesium was studied in an unsaturated core of Callovo-Oxfordian claystone, which is a potential host rock for retrievable disposal of high-level radioactive wastes. In-diffusion laboratory experiments were performed on rock samples with water saturation degrees ranging from 81% to 100%. The analysis of both cesium concentration monitoring in the source reservoir and post-mortem cesium rock concentration profile of the samples was carried out using a chemical-transport code where the sorption of cesium was described by a multisite ion-exchange model. The results showed that cesium exhibited a clear trend related to the saturation degree of the sample. The more dehydrated the rock sample, the slower the decrease of cesium concentration, and the thinner the penetration depth of cesium was. The effective diffusion coefficient (De) for cesium decreased from 18.5 × 10(-11) m(2) s(-1) at full-saturation to 0.3 × 10(-11) m(2) s(-1) for the more dehydrated sample. This decrease is almost 1 order of magnitude higher than that for tritiated water (HTO), although a similar behavior could have been expected, since cesium is known to diffuse in the same parts of the pore space as HTO in fully saturated claystones.     

Effect of saline waste solution infiltration rates on uranium retention and spatial distribution in Hanford sediments

The accidental overfilling of waste liquid from tank BX-102 at the Hanford Site in 1951 put about 10 t of U(VI) into the vadose zone. In order to understand the dominant geochemical reactions and transport processes that occurred during the initial infiltration and to help understand current spatial distribution, we simulated the waste liquid spilling event in laboratory sediment columns using synthesized metal waste solution. We found that, as the plume propagated through sediments, pH decreased greatly (as much as 4 units) at the moving plume front. Infiltration flow rates strongly affect U behavior. Slower flow rates resulted in higher sediment-associated U concentrations, and higher flow rates (> or =5 cm/day) permitted practically unretarded U transport. Therefore, given the very high Ksat of most of Hanford formation, the low permeability zones within the sediment could have been most important in retaining high concentrations of U during initial release into the vadose zone. Massive amount of colloids, including U-colloids, formed at the plume fronts. Total U concentrations (aqueous and colloid) within plume fronts exceeded the source concentration by up to 5-fold. Uranium colloid formation and accumulation at the neutralized plume front could be one mechanism responsible for highly heterogeneous U distribution observed in the contaminated Hanford vadose zone.     

Pore-scale quantification of colloid transport in saturated porous media

It is currently not clear how to quantifiably relate pore-scale observations of colloid transportto larger scales, so,we proposed a geometric theory showing that pore-scale-derived rate constants may be appropriate to model a larger scale system. This study considered three different types of colloids: latex microspheres, Escherichia coli, and microspheres made of poly lactic acid (PLA). Colloid attachment and detachment rate constants were calculated using digital microscope images, taken in rapid (1 s) sequences, from which rates of attaching and detaching colloids were readily observed. Average rate constants from >1000 images per colloid-type were used to model Darcy-scale colloid transport breakthrough curves. The modeled and observed breakthrough curves agreed well for all three types of colloids. However, for latex and PLA microspheres, the model systematically under predicted the breakthrough curves' rising limb, which may indicate that the rate "constants" are actually dependent on the amount of attached colloids. Insights into these sorts of complexities are best addressed by research that considers both pore-scale phenomena and larger-scale transport responses.     

Spectroscopic evidence for uranium bearing precipitates in vadose zone sediments at the Hanford 300-area site

Uranium (U) solid-state speciation in vadose zone sediments collected beneath the former North Process Pond (NPP) in the 300 Area of the Hanford site (Washington) was investigated using multi-scale techniques. In 30 day batch experiments, only a small fraction of total U (approximately 7.4%) was released to artificial groundwater solutions equilibrated with 1% pCO2. Synchrotron-based micro-X-rayfluorescence spectroscopy analyses showed that U was distributed among at least two types of species: (i) U discrete grains associated with Cu and (ii) areas with intermediate U concentrations on grains and grain coatings. Metatorbernite (Cu[UO2]2[PO4]2 x 8H2O) and uranophane (Ca[UO2]2[SiO3(OH)]2 x 5H2O) at some U discrete grains, and muscovite at U intermediate concentration areas, were identified in synchrotron-based micro-X-ray diffraction. Scanning electron microscopy/energy dispersive X-ray analyses revealed 8-10 microm size metatorbernite particles that were embedded in C-, Al-, and Si-rich coatings on quartz and albite grains. In mu- and bulk-X-ray absorption structure (mu-XAS and XAS) spectroscopy analyses, the structure of metatorbernite with additional U-C and U-U coordination environments was consistently observed at U discrete grains with high U concentrations. The consistency of the mu- and bulk-XAS analyses suggests that metatorbernite may comprise a significant fraction of the total U in the sample. The entrapped, micrometer-sized metatorbernite particles in C-, Al-, and Si-rich coatings, along with the more soluble precipitated uranyl carbonates and uranophane, likely control the long-term release of U to water associated with the vadose zone sediments.     

In situ colloid mobilization in Hanford sediments under unsaturated transient flow conditions: effect of irrigation pattern

Colloid transport may facilitate off-site transport of radioactive wastes at the Hanford site, Washington State. In this study, column experiments were conducted to examine the effect of irrigation schedule on releases of in situ colloids from two Hanford sediments during saturated and unsaturated transientflow and its dependence on solution ionic strength, irrigation rate, and sediment texture. Results show that transient flow mobilized more colloids than steady-state flow. The number of short-term hydrological pulses was more important than total irrigation volume for increasing the amount of mobilized colloids. This effect increased with decreasing ionic strength. At an irrigation rate equal to 5% of the saturated hydraulic conductivity, a transient multipulse flow in 100 mM NaNO3 was equivalent to a 50-fold reduction of ionic strength (from 100 mM to 2 mM) with a single-pulse flow in terms of their positive effects on colloid mobilization. Irrigation rate was more important for the initial release of colloids. In addition to water velocity, mechanical straining of colloids was partly responsible for the smaller colloid mobilization in the fine than in the coarse sands, although the fine sand contained much larger concentrations of colloids than the coarse sand.     

Colloid transport in a heterogeneous partially saturated sand column

Colloid transport was studied in heterogeneous sand columns under unsaturated steady-state conditions, using two sizes of acid-cleaned sand to pack the column. Heterogeneity was created by placing three continuous tubes of fine sand (3.6% of the total volume) within a column of coarse sand (mean grain diameters 0.36 and 1.2 mm, respectively). Experiments were performed under three flow rates (0.1, 0.2, and 0.4 cm/ min) applied by a rain simulator atthe top of the column. Constant water-content profile in the coarse sand was achieved by applying corresponding suction at the column bottom. Three sizes of latex microspheres (1, 0.2, and 0.02 microm) and soluble tracers (LiBr), diluted in a weak base (pH 7.3, ionic strength 0.0023 M) solution, were used simultaneously. Introduction of preferential pathways reduced front-arrival time about 2-fold and increased colloid recovery which, at the 0.2 cm/min flow rate, was higher than at 0.4 and 0.1 cm/min. Maximum solution flux from coarse to fine sand (due to differences in matric pressure) at 0.2 cm/min, verified by hydrodynamic modeling, could explain this phenomenon. Results suggest that in heterogeneous soil, maximum colloid recovery does not necessarily occur at maximum water content. This has clear implications for colloid transport in natural soils, many of which are heterogeneous.     

In situ X-ray diffraction study of Na+ saturated montmorillonite exposed to variably wet super critical CO2

Reactions involving variably hydrated super critical CO(2) (scCO(2)) and a Na saturated dioctahedral smectite (Na-STX-1) were examined by in situ high-pressure X-ray diffraction at 50 °C and 90 bar, conditions that are relevant to long-term geologic storage of CO(2). Both hydration and dehydration reactions were rapid with appreciable reaction occurring in minutes and near steady state occurring within an hour. Hydration occurred stepwise as a function of increasing H(2)O in the system; 1W, 2W-3W, and >3W clay hydration states were stable from ~2-30%, ~31-55 < 64%, and ≥ ~71% H(2)O saturation in scCO(2), respectively. Exposure of sub 1W clay to anhydrous scCO(2) caused interlayer expansion, not contraction as expected for dehydration, suggesting that CO(2) intercalated the interlayer region of the sub 1W clay, which might provide a secondary trapping mechanism for CO(2). In contrast, control experiments using pressurized N(2) and similar initial conditions as in the scCO(2) study, showed little to no change in the d(001) spacing, or hydration states, of the clay. A salient implication for cap rock integrity is that clays can dehydrate when exposed to wet scCO(2). For example, a clay in the ~3W hydration state could collapse by ~3 ? in the c* direction, or ~15%, if exposed to scCO(2) at less than or equal to about 64% H(2)O saturation.     

Advective removal of intraparticle uranium from contaminated vadose zone sediments, Hanford, U.S

A column study on U(VI)-contaminated vadose zone sediments from the Hanford Site, WA, was performed to investigate U(VI) release kinetics with water advection and variable geochemical conditions. The sediments were collected from an area adjacent to and below tank BX-102 that was contaminated as a result of a radioactive tank waste overfill event. The primary reservoir for U(VI) in the sediments are micrometer-size precipitates composed of nanocrystallite aggregates of a Na-U-Silicate phase, most likely Na-boltwoodite, that nucleated and grew within microfractures of the plagioclase component of sand-sized granitic clasts. Two sediment samples, with different U(VI) concentrations and intraparticle mass transfer properties, were leached with advective flows of three different solutions. The influent solutions were all calcite-saturated and in equilibrium with atmospheric CO2. One solution was prepared from DI water, the second was a synthetic groundwater (SGW) with elevated Na that mimicked groundwater at the Hanford site, and the third was the same SGW but with both elevated Na and Si. The latter two solutions were employed, in part, to test the effect of saturation state on U(VI) release. For both sediments, and all three electrolytes, there was an initial rapid release of U(VI) to the advecting solution followed by slower near steady-state release. U(VI)aq concentrations increased during subsequent stop-flow events. The electrolytes with elevated Na and Si depressed U(VL)aq concentrations in effluent solutions. Effluent U(VI)aq concentrations for both sediments and all three electrolytes were simulated reasonably well by a three domain model (the advecting fluid, fractures, and matrix) that coupled U(VI) dissolution, intraparticle U(VI)aq diffusion, and interparticle advection, where diffusion and dissolution properties were parameterized in a previous batch study.     

Kinetic desorption and sorption of U(VI) during reactive transport in a contaminated Hanford sediment

Column experiments were conducted to investigate U(VI) desorption and sorption kinetics in a sand-textured, U(VI)-contaminated (22.7 micromol kg(-1)) capillary fringe sediment from the U.S. Department of Energy (DOE) Hanford site. Saturated column experiments were performed under mildly alkaline conditions representative of the Hanford site where uranyl-carbonate and calcium-uranyl-carbonate complexes dominate aqueous speciation. A U(VI)-free solution was used to study contaminant U(VI) desorption in columns where different flow rates were applied. Sorbed, contaminant U(VI) was partially labile (11.8%), and extended leaching times and water volumes were required for complete desorption of the labile fraction. Uranium-(VI) sorption was studied after the desorption of labile, contaminant U(VI) using different U(VI) concentrations in the leaching solution. Strong kinetic effects were observed for both U(VI) sorption and desorption, with half-life ranging from 8.5 to 48.5 h for sorption and from 39.3 to 150 h for desorption. Although U(VI) is semi-mobile in mildly alkaline, subsurface environments, we observed substantial U(VI) adsorption, significant retardation during transport, and atypical breakthrough curves with extended tailing. A distributed rate model was applied to describe the effluent data and to allow comparisons between the desorption rate of contaminant U(VI) with the rate of shortterm U(VI) sorption. Desorption was the slower process. We speculate that the kinetic behavior results from transport or chemical phenomena within the phyllosilicate-dominated fine fraction present in the sediment. Our results suggest that U(VI) release and transport in the vadose zone and aquifer system from which the sediment was obtained are kinetically controlled.     

In-situ measurements of engineered nanoporous particle transport in saturated porous media

Engineered nanoporous particles have become an important class of nanostructured materials that have been increasingly applied in energy, biomedical, and environmental researches and industries. The internal pore surfaces in the particles can be chemically functionalized for environmental applications to sequestrate metals and radionuclide contaminants from groundwater. The fate and transport of the nanoporous particles in subsurface environments, however, have not been studied. Here we present a scanning optical fiber fluorescence profiler that can be used to in situ monitor the transport of fluorescent particles in column systems. Engineered nanoporous silicate particles (ENSPs) that were covalently bounded with fluorescence-emitting, and uranium-chelating ligands in the intraparticle pore domains were synthesized and used as an example to investigate nanoporous particle transport and to demonstrate the application of the developed in situ measurement profiler. The profiler detected an "irreversible" or slowly detached fraction of ENSPs in a sand collector even under thermodynamically unfavorable conditions for particle attachment. Further, the in situ measurement system detected the spatial variability of ENSPs transport that deviated from one-dimensional, homogeneous assumption, which is typically used to model particle transport in column systems. Generally, however, both measured and model-calculated results indicated that the transport of ENSPs was consistent with that of nonporous colloidal particles subjected to coupled reversible attachment/detachment and straining processes. The developed system can also be applied to detect other fluorescent nanostructured or colloidal particles in porous media.     

Spectroscopic and diffraction study of uranium speciation in contaminated vadose zone sediments from the Hanford site, Washington state

Contamination of vadose zone sediments under tank BX-102 at the Hanford site, Washington, resulted from the accidental release of 7-8 metric tons of uranium dissolved in caustic aqueous sludge in 1951. We have applied synchrotron-based X-ray spectroscopic and diffraction techniques to characterize the speciation of uranium in samples of these contaminated sediments. UIII-edge X-ray absorption fine structure (XAFS) spectroscopic studies demonstrate that uranium occurs predominantly as a uranium(VI) silicate from the uranophane group of minerals. XAFS cannot distinguish between the members of this mineral group due to the near identical local coordination environments of uranium in these phases. However, these phases differ crystallographically, and can be distinguished using X-ray diffraction (XRD) methods. As the concentration of uranium was too low for conventional XRD to detect these phases, X-ray microdiffraction (microXRD) was used to collect diffraction patterns on approximately 20 microm diameter areas of localized high uranium concentration found using microscanning X-ray fluorescence (microSXRF). Only sodium boltwoodite, Na(UO2)(SiO3OH) x 1.5H20, was observed; no other uranophane group minerals were present. Sodium boltwoodite formation has effectively sequestered uranium in these sediments under the current geochemical and hydrologic conditions. Attempts to remediate the uranium contamination will likely face significant difficulties because of the speciation and distribution of uranium in the sediments.     

Uranium reduction in sediments under diffusion-limited transport of organic carbon

Costly disposal of uranium (U) contaminated sediments is motivating research on in situ U(VI) reduction to insoluble U(IV) via directly or indirectly microbially mediated pathways. Delivery of organic carbon (OC) into sediments for stimulating U bioreduction is diffusion-limited in less permeable regions of the subsurface. To study OC-based U reduction in diffusion-limited regions, one slightly acidic and another calcareous sediment were treated with uranyl nitrate, packed into columns, then hydrostatically contacted with tryptic soy broth solutions. Redox potentials, U oxidation state, and microbial communities were well correlated. At average supply rates of 0.9 micromol OC (g sediment)(-1) day(-1), the U reduction zone extended to only about35-45 mm into sediments. The underlying unreduced U(VI) zone persisted over 600 days because the supply of OC was diffusion-limited and metabolized within a short distance. These results also suggestthat low U concentrations in groundwater samples from OC-treated sediments are not necessarily indicative of pervasive U reduction because interior and exterior regions of such sediment blocks can contain primarily U(VI) and U(IV), respectively.