Influence of calcium carbonate on U(VI) sorption to soils

The high stability of calcium uranyl carbonate complexes in the circumneutral pH range has a strong impact on U(VI) sorption in calcareous soils. To quantify this influence, sorption of U(VI) to soils in the presence of naturally occurring calcium carbonate was investigated by conducting batch experiments in which either U(VI) concentration or solution pH was varied. Two soils containing different calcium carbonate concentrations were selected, one from Oak Ridge, TN, and another from Altamont Pass, CA. The results show that the presence of calcium carbonate in soils strongly affects U(VI) sorption. Higher concentrations of soil calcium carbonate lead to a pronounced suppression of the pH-dependent sorption curve in the neutral pH range because of the formation of a very stable neutral complex of calcium uranyl carbonate in solution. A surface complexation model considering both strong and weak sites for ferrihydrite and ionizable hydroxyl sites for clay minerals was compared with experimental results, and U(VI) binding parameters were reasonably estimated. Fair agreement was found between the model predictions and sorption data, which span a wide range of U(VI) concentrations and pH. The results also show that appropriate solution-to-solid ratios need to be used when measuring distribution coefficients in calcareous soils to avoid complete CaCO3 dissolution and consequent dilution of calcium uranyl carbonate complexes.     

U(VI) adsorption to heterogeneous subsurface media: application of a surface complexation model

The pH-dependent adsorption of U(VI) onto three heterogeneous, subsurface media from the Department of Energy (DOE) Oak Ridge Reservation, Savannah River Site, and Hanford Reservation was investigated. The three materials contained significant quantities of iron and manganese oxides with nearly identical extractable iron oxide contents (25.3-25.8 g/kg). A model independently developed for the adsorption of U(VI) to synthetic ferrihydrite (Waite, T. D.; Davis, J. A.; Payne, T. E.; Waychunas, G. A.; Xu, N. Geochim. Cosmochim. Acta 1994, 58, 5465-5478) was able to predict the major features of the pH-dependent U(VI) adsorption to the materials under the assumption that all the dithionite-citrate-bicarbonate extractable iron oxide was present as ferrihydrite. Further experiments with the Oak Ridge soil as a function of carbonate and U(VI) concentration indicated that the model could predict pH-dependent U(VI) adsorption to within a root mean square error of 0.163-0.408, even under conditions outside of those for which the model was developed. These results indicate that this model could be used as a first approximation in predicting U(VI) adsorption and transport in the subsurface. U(VI) adsorption also decreased at pH >10, even in the absence of carbonate, which is of potential importance to U(VI) mobility in extreme environments present in the subsurface at some DOE facilities. The pH-dependent adsorption of U(VI) was fundamentally different in systems with a constant CO2 partial pressure as compared to a constant total carbonate concentration. Experiments at constant CO2 partial pressure may not be representative of the conditions present in the subsurface, and a constant carbonate concentration does not always result in decreased U(VI) adsorption at higher pH values.     

Molecular-scale structure of uranium(VI) immobilized with goethite and phosphate

The molecular-scale immobilization mechanisms of uranium uptake in the presence of phosphate and goethite were examined by extended X-ray absorption fine structure (EXAFS) spectroscopy. Wet chemistry data from U(VI)-equilibrated goethite suspensions at pH 4-7 in the presence of ~100 μM total phosphate indicated changes in U(VI) uptake mechanisms from adsorption to precipitation with increasing total uranium concentrations and with increasing pH. EXAFS analysis revealed that the precipitated U(VI) had a structure consistent with the meta-autunite group of solids. The adsorbed U(VI), in the absence of phosphate at pH 4-7, formed bidentate edge-sharing, ≡ Fe(OH)(2)UO(2), and bidentate corner-sharing, (≡ FeOH)(2)UO(2), surface complexes with respective U-Fe coordination distances of ~3.45 and ~4.3 ?. In the presence of phosphate and goethite, the relative amounts of precipitated and adsorbed U(VI) were quantified using linear combinations of the EXAFS spectra of precipitated U(VI) and phosphate-free adsorbed U(VI). A U(VI)-phosphate-Fe(III) oxide ternary surface complex is suggested as the dominant species at pH 4 and total U(VI) of 10 μM or less on the basis of the linear combination fitting, a P shell indicated by EXAFS, and the simultaneous enhancement of U(VI) and phosphate uptake on goethite. A structural model for the ternary surface complex was proposed that included a single phosphate shell at ~3.6 ? (U-P) and a single iron shell at ~4.3 ? (U-Fe). While the data can be explained by a U-bridging ternary surface complex, (≡ FeO)(2)UO(2)PO(4), it is not possible to statistically distinguish this scenario from one with P-bridging complexes also present.     

Cryogenic laser induced fluorescence characterization of U(VI) in Hanford Vadose Zone pore waters

Ambient and liquid helium temperature laser-induced time-resolved uranyl fluorescence spectroscopy was applied to study the speciation of aqueous uranyl solutions containing carbonate and phosphate and two porewater samples obtained by ultracentrifugation of U(VI)-contaminated sediments. The significantly enhanced fluorescence signal intensity and spectral resolution found at liquid helium temperature allowed, for the first time, direct fluorescence spectroscopic observation of the higher aqueous uranyl complexes with carbonate: UO2(CO3)2(2-), UO2(CO3)3(4-), and (UO2)2(OH)3CO3-. The porewater samples were nonfluorescent at room temperature. However, at liquid helium temperature, both porewater samples displayed strong, well-resolved fluorescence spectra. Comparisons of the spectroscopic characteristics of the porewaters with those of the standard uranyl-carbonate complexes confirmed that U(VI) in the porewaters existed primarily as UO2(CO3)3(4-) along with a small amount of other minor components, such as dicalcium-urano-tricarbonate complex, Ca2UO2(CO3)3, consistent with thermodynamic calculation. The U(VI)-carbonate complex is apparently the mobile species responsible for the subsurface migration of U(VI), even though the majority of the in-ground U(VI) inventory at the site from which the samples were obtained exists as intragrain U(VI)-silicate precipitates.     

U(VI)-kaolinite surface complexation in absence and presence of humic acid studied by TRLFS

Time-resolved laser-induced fluorescence spectroscopy (TRLFS) was applied to study the U(VI) surface complexes on kaolinite in the presence and absence of humic acid (HA). Two uranyl surface species with fluorescence lifetimes of 5.9 +/- 1.4 and 42.5 +/- 3.4 micros and 4.4 +/- 1.2 and 30.9 +/- 7.2 micros were identified in the binary (U(VI)-kaolinite) and ternary system (U(VI)-HA-kaolinite), respectively. The fluorescence spectra of adsorbed uranyl surface species are described with six and five fluorescence emission bands in the binary and ternary system, respectively. The positions of peak maxima are shifted significantly to higher wavelengths compared to the free uranyl ion in perchlorate medium. HA has no influence on positions of the fluorescence emission bands. In the binary system, both surface species can be attributed to adsorbed bidentate mononuclear surface complexes, which differ in the number of water molecules in their coordination environment. In the ternary system, U(VI) prefers direct binding on kaolinite rather than via HA, but it is sorbed as a uranyl-humate complex. Consequently, the hydration shell of the U(VI) surface complexes is displaced with complexed HA, which is simultaneously distributed between kaolinite particles. Aluminol binding sites are assumed to control the sorption of U(VI) onto kaolinite.     

Photodegradation of a ternary iron(III)-uranium(VI)-citric acid complex

The mechanisms of photodegradation of binary iron- and uranium-citrate and ternary iron-uranium-citrate complexes were elucidated. Citric acid degradation products were identified by HPLC and GC, and the metal precipitates were identified by XRD and EXAFS. Photodegradation of a binuclear iron-citrate complex occurred as a result of two one-electron oxidations of citric acid with the formation of 3-oxoglutarate and two ferrous ions. The ferrous ions were reoxidized by a photo-Fenton reaction, resulting in the precipitation of iron as two-line ferrihydrite Fe(OH)3. The citric acid in the uranium-citrate complex underwent a two-electron oxidation to acetoacetate with the concomitant reduction of U(VI) to U(IV). The U(IV) was subsequently photooxidized in the presence of dioxygen with precipitation of uranium as the mineral schoepite (UO3 x 2H2O). A two-step electron reduction of two ferric ions to two ferrous ions wasthe primary mechanism for photodegradation of the ternary iron-uranium-citrate complex with oxidation of citric acid to 3-oxoglutarate; reduction of uranium was not observed. The iron precipitated as ferrihydrite and the uranyl ion as a uranyl hydroxide species. These results show the potential application of photochemical treatment of wastewater and decontamination solutions containing binary and ternary iron- and uranium-citrate complexes.     

Molecular-scale characterization of uranium sorption by bone apatite materials for a permeable reactive barrier demonstration

Uranium binding to bone charcoal and bone meal apatite materials was investigated using U L(III)-edge EXAFS spectroscopy and synchrotron source XRD measurements of laboratory batch preparations in the absence and presence of dissolved carbonate. Pelletized bone char apatite recovered from a permeable reactive barrier (PRB) at Fry Canyon, UT, was also studied. EXAFS analyses indicate that U(VI) sorption in the absence of dissolved carbonate occurred by surface complexation of U(VI) for sorbed concentrations < or = 5500 microg U(VI)/g for all materials with the exception of crushed bone char pellets. Either a split or a disordered equatorial oxygen shell was observed, consistent with complexation of uranyl by the apatite surface. A second shell of atoms at a distance of 2.9 A was required to fit the spectra of samples prepared in the presence of dissolved carbonate (4.8 mM total) and is interpreted as formation of ternary carbonate complexes with sorbed U(VI). A U-P distance at 3.5-3.6 A was found for most samples under conditions where uranyl phosphate phases did not form, which is consistent with monodentate coordination of uranyl by phosphate groups in the apatite surface. At sorbed concentrations > or = 5500 microg U(VI)/g in the absence of dissolved carbonate, formation of the uranyl phosphate solid phase, chernikovite, was observed. The presence of dissolved carbonate (4.8 mM total) suppressed the formation of chernikovite, which was not detected even with sorbed U(VI) up to 12,300 microg U(VI)/g in batch samples of bone meal, bone charcoal, and reagent-grade hydroxyapatite. EXAFS spectra of bone char samples recovered from the Fry Canyon PRB were comparable to laboratory samples in the presence of dissolved carbonate where U(VI) sorption occurred by surface complexation. Our findings demonstrate that uranium uptake by bone apatite will probably occur by surface complexation instead of precipitation of uranyl phosphate phases under the groundwater conditions found at many U-contaminated sites.     

Speciation-dependent microbial reduction of uranium within iron-coated sands

Transport of uranium within surface and subsurface environments is predicated largely on its redox state. Uranyl reduction may transpire through either biotic (enzymatic) or abiotic pathways; in either case, reduction of U(VI) to U(IV) results in the formation of sparingly soluble UO2 precipitates. Biological reduction of U(VI), while demonstrated as prolific under both laboratory and field conditions, is influenced by competing electron acceptors (such as nitrate, manganese oxides, or iron oxides) and uranyl speciation. Formation of Ca-UO2-CO3 ternary complexes, often the predominate uranyl species in carbonate-bearing soils and sediments, decreases the rate of dissimilatory U(VI) reduction. The combined influence of uranyl speciation within a mineralogical matrix comparable to natural environments and under hydrodynamic conditions, however, remains unresolved. We therefore examined uranyl reduction by Shewanella putrefaciens within packed mineral columns of ferrihydrite-coated quartz sand under conditions conducive or nonconducive to Ca-UO2-CO3 species formation. The results are dramatic. In the absence of Ca, where uranyl carbonato complexes dominate, U(VI) reduction transpires and consumes all of the U(VI) within the influent solution (0.166 mM) over the first 2.5 cm of the flow field for the entirety of the 54 d experiment. Over 2 g of U is deposited during this reaction period, and despite ferrihydrite being a competitive electron acceptor, uranium reduction appears unabated for the duration of our experiments. By contrast, in columns with 4 mM Ca in the influent solution (0.166 mM uranyl), reduction (enzymatic or surface-bound Fe(III) mediated) appears absent and breakthrough occurs within 18 d (at a flow rate of 3 pore volumes per day). Uranyl speciation, and in particular the formation of ternary Ca-UO2-CO3 complexes, has a profound impact on U(VI) reduction and thus transport within anaerobic systems.     

Adsorbed U(VI) surface species on muscovite identified by laser fluorescence spectroscopy and transmission electron microscopy

Time-resolved laser-induced fluorescence spectroscopy (TRLFS) and high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) were applied to investigate the species of uranyl(VI) adsorbed onto muscovite platelets and muscovite suspensions (grain size: 63-200 microm). TRLFS provided evidence for the presence of two adsorbed uranium(VI) surface species on edge-surfaces of muscovite. The two species showed different positions of the fluorescence emission bands and different fluorescence lifetimes indicating a different coordination environment for the two species. HAADF-STEM revealed that nanoclusters of an amorphous uranium phase were attached to the edge-surfaces of muscovite powder during batch sorption experiments. These U-nanoclusters were not observed on {00/} cleavage planes of the muscovite. The surface species with the shorter fluorescence lifetimes are interpreted as truly adsorbed bidentate surface complexes, in which the U(VI) binds to aluminol groups of edge-surfaces. The surface species with the longer fluorescence lifetimes are interpreted to be an amorphous U(VI) condensate or nanosized clusters of polynuclear uranyl(VI) surface species with a particle diameter of 1 to 2 nm. Depending on the size of these clusters the fluorescence lifetimes vary; i.e., the larger the nanosized clusters, the longer is the fluorescence lifetime.     

Identification of simultaneous U(VI) sorption complexes and U(IV) nanoprecipitates on the magnetite (111) surface

Sequestration of uranium (U) by magnetite is a potentially important sink for U in natural and contaminated environments. However, molecular-scale controls that favor U(VI) uptake including both adsorption of U(VI) and reduction to U(IV) by magnetite remain poorly understood, in particular, the role of U(VI)-CO(3)-Ca complexes in inhibiting U(VI) reduction. To investigate U uptake pathways on magnetite as a function of U(VI) aqueous speciation, we performed batch sorption experiments on (111) surfaces of natural single crystals under a range of solution conditions (pH 5 and 10; 0.1 mM U(VI); 1 mM NaNO(3); and with or without 0.5 mM CO(3) and 0.1 mM Ca) and characterized surface-associated U using grazing incidence extended X-ray absorption fine structure spectroscopy (GI-EXAFS), grazing incidence X-ray diffraction (GI-XRD), and scanning electron microscopy (SEM). In the absence of both carbonate ([CO(3)](T), denoted here as CO(3)) and calcium (Ca), or in the presence of CO(3) only, coexisting adsorption of U(VI) surface species and reduction to U(IV) occurs at both pH 5 and 10. In the presence of both Ca and CO(3), only U(VI) adsorption (VI) occurs. When U reduction occurs, nanoparticulate UO(2) forms only within and adjacent to surface microtopographic features such as crystal boundaries and cracks. This result suggests that U reduction is limited to defect-rich surface regions. Further, at both pH 5 and 10 in the presence of both CO(3) and Ca, U(VI)-CO(3)-Ca ternary surface species develop and U reduction is inhibited. These findings extend the range of conditions under which U(VI)-CO(3)-Ca complexes inhibit U reduction.     

Effects of phosphate on uranium(VI) adsorption to goethite-coated sand

U(VI)-phosphate interactions are important in governing the subsurface mobility of U(VI) in both natural and contaminated environments. We studied U(VI) adsorption on goethite-coated sand (to mimic natural Fe-coated subsurface materials) as a function of pH in systems closed to the atmosphere, in both the presence and the absence of phosphate. Our results indicate that phosphate strongly affects U(VI) adsorption. The effect of phosphate on U(VI) adsorption was dependent on solution pH. At low pH, the adsorption of U(VI) increased in the presence of phosphate, and higher phosphate concentration caused a larger extent of increase in U(VI) adsorption. Phosphate was strongly bound by the goethite surface in the low pH range, and the increased adsorption of U(VI) at low pH was attributed to the formation of ternary surface complexes involving both U(VI) and phosphate. In the high pH range, the adsorption of U(VI) decreased in the presence of phosphate at low total Fe concentration, and higher phosphate concentration caused a larger extent of decrease in U(VI) adsorption. This decrease in U(VI) adsorption was attributed to the formation of soluble uranium-phosphate complexes. A surface complexation model (SCM) was proposed to describe the effect of phosphate on U(VI) adsorption to goethite. This proposed model was based on previous models that predict U(VI) adsorption to iron oxides in the absence of phosphate and previous models developed to predict phosphate adsorption on goethite. A postulated ternary surface complex of the form of (>FePO4UO2) was included in our model to account for the interactions between U(VI) and phosphate. The model we established can successfully predict U(VI) adsorption in the presence of phosphate under a range of conditions (i.e., pH, total phosphate concentration, and total Fe concentration).     

Adsorption mechanism of arsenic on nanocrystalline titanium dioxide

Arsenate [As(V)] and arsenite [As(III)] interactions at the solid-water interface of nanocrystalline TiO2 were investigated using electrophoretic mobility (EM) measurements, Fourier transform infrared (FTIR) spectroscopy, extended X-ray absorption fine structure (EXAFS) spectroscopy, and surface complexation modeling. The adsorption of As(V) and As(III) decreased the point of zero charge of TiO2 from 5.8 to 5.2, suggesting the formation of negatively charged inner-sphere surface complexes for both arsenic species. The EXAFS analyses indicate that both As(V) and As(III) form bidentate binuclear surface complexes as evidenced by an average Ti-As(V) bond distance of 3.30 A and Ti-As(III) bond distance of 3.35 A. The FTIR bands caused by vibrations of the adsorbed arsenic species remained at the same energy levels at different pH values. Consequently, the surface complexes on TiO2 maintained the same nonprotonated speciation at pH values from 5 to 10, and the dominant surface species were (TiO)2AsO2- and (TiO)2AsO- for As(V) and As(III), respectively. The surface configurations constrained with the spectroscopic results were formulated in the diffuse layer model to describe the adsorption behavior of As in the pH range between 4 and 12. The study suggests that TiO2 is an effective adsorbent for As removal due to its high surface area and the presence of high affinity surface hydroxyl groups.     

Influence of sediment bioreduction and reoxidation on uranium sorption

The influence of sediment bioreduction and reoxidation on U(VI) sorption was studied using Fe(II) oxide-containing saprolite from the U.S. Department of Energy (DOE) Oak Ridge site. Bioreduced sediments were generated by anoxic incubation with a metal-reducing bacterium, Shewanella putrefaciens strain CN32, supplied with lactate as an electron donor. The reduced sediments were subsequently reoxidized by air contact. U(VI) sorption was studied in NaNO3-HCO3 electrolytes that were both closed and open to atmosphere and where pH, U(VI), and carbonate concentration were varied. M?ssbauer spectroscopy and chemical analyses showed that 50% of the Fe(III)-oxides were reduced to Fe(II) that was sorbed to the sediment during incubation with CN32. However, this reduction and subsequent reoxidation of the sorbed Fe(II) had negligible influence on the rate and extent of U sorption or the extractability of sorbed U by 0.2 mol/L NaHCO3. Various results indicated that U(VI) surface complexation was the primary process responsible for uranyl sorption by the bioreduced and reoxidized sediments. A two-site, nonelectrostatic surface complexation model best described U(VI) adsorption under variable pH, carbonate, and U(VI) conditions. A ferrihydrite-based diffuse double layer model provided a better estimation of U(VI) adsorption without parameter adjustment than did a goethite-based model, even though a majority of the Fe(III)-oxides in the sediments were goethite. Our results highlight the complexity of the coupled U-Fe redox system and show that sorbed Fe(II) is not a universal reductant for U(VI) as commonly assumed.     

Thermodynamic constraints on the oxidation of biogenic UO2 by Fe(III) (Hydr)oxides

Uranium mobility in the environment is partially controlled by its oxidation state, where it exists as either U(VI) or U(IV). In aerobic environments, uranium is generally found in the hexavalent form, is quite soluble, and readily forms complexes with carbonate and calcium. Under anaerobic conditions, common metal respiring bacteria can reduce soluble U(VI) species to sparingly soluble UO2 (uraninite); stimulation of these bacteria, in fact, is being explored as an in situ uranium remediation technique. However, the stability of biologically precipitated uraninite within soils and sediments is not well characterized. Here we demonstrate that uraninite oxidation by Fe(III) (hydr)oxides is thermodynamically favorable under limited geochemical conditions. Our analysis reveals that goethite and hematite have a limited capacity to oxidize UO2(biogenic) while ferrihydrite can lead to UO2(biogenic) oxidation. The extent of UO2(biogenic) oxidation by ferrihydrite increases with increasing bicarbonate and calcium concentration, but decreases with elevated Fe(II)(aq) and U(VI)(aq) concentrations. Thus, our results demonstrate that the oxidation of UO2(biogenic) by Fe(III) (hydr)oxides may transpire under mildly reducing conditions when ferrihydrite is present.     

Water structure and aqueous uranyl(VI) adsorption equilibria onto external surfaces of beidellite, montmorillonite, and pyrophyllite: results from molecular simulations

Molecular dynamics simulations were performed to provide a systematic study of aqueous uranyl adsorption onto the external surface of 2:1 dioctahedral clays. Our understanding of this key process is critical in predicting the fate of radioactive contaminants in natural groundwaters. These simulations provide atomistic detail to help explain experimental trends in uranyl adsorption onto natural media containing smectite clays. Aqueous uranyl concentrations ranged from 0.027 to 0.162 M. Sodium ions and carbonate ions (0.027-0.243 M) were also present in the aqueous regions to more faithfully model a stream of uranyl-containing groundwater contacting a mineral system comprised of Na-smectite. No adsorption occurred near the pyrophyllite surface, and there was little difference in uranyl adsorption onto the beidellite and montmorillonite, despite the difference in location of clay layer charge between the two. At low uranyl concentration, the pentaaquouranyl complex dominates in solution and readily adsorbs to the clay basal plane. At higher uranyl (and carbonate) concentrations, the mono(carbonato) complex forms in solution, and uranyl adsorption decreases. Sodium adsorption onto beidellite occurred both as inner- and outer-sphere surface complexes, again with little effect on uranyl adsorption. Uranyl surface complexes consisted primarily of the pentaaquo cation (85%) and to a lesser extent the mono(carbonato) species (15%). Speciation diagrams of the aqueous region indicate that the mono(carbonato)uranyl complex is abundant at high ionic strength. Oligomeric uranyl complexes are observed at high ionic strength, particularly near the pyrophyllite and montmorillonite surfaces. Atomic density profiles of water oxygen and hydrogen atoms are nearly identical near the beidellite and montmorillonite surfaces. Water structure therefore appears to be governed by the presence of adsorbed ions and not by the location of layer charge associated with the substrate. The water oxygen density near the pyrophyllite surface is similar to the other cases, but the hydrogen density profile indicates reduced hydrogen bonding between adsorbed water molecules and the surface.     

Pilot-scale in situ bioremedation of uranium in a highly contaminated aquifer. 2. Reduction of u(VI) and geochemical control of u(VI) bioavailability

In situ microbial reduction of soluble U(VI) to sparingly soluble U(IV) was evaluated at the site of the former S-3 Ponds in Area 3 of the U.S. Department of Energy Natural and Accelerated Bioremediation Research Field Research Center, Oak Ridge, TN. After establishing conditions favorable for bioremediation (Wu, et al. Environ. Sci. Technol. 2006, 40, 3988-3995), intermittent additions of ethanol were initiated within the conditioned inner loop of a nested well recirculation system. These additions initially stimulated denitrification of matrix-entrapped nitrate, but after 2 months, aqueous U levels fell from 5 to approximately 1 microM and sulfate reduction ensued. Continued additions sustained U(VI) reduction over 13 months. X-ray near-edge absorption spectroscopy (XANES) confirmed U(VI) reduction to U(IV) within the inner loop wells, with up to 51%, 35%, and 28% solid-phase U(IV) in sediment samples from the injection well, a monitoring well, and the extraction well, respectively. Microbial analyses confirmed the presence of denitrifying, sulfate-reducing, and iron-reducing bacteria in groundwater and sediments. System pH was generally maintained at less than 6.2 with low bicarbonate level (0.75-1.5 mM) and residual sulfate to suppress methanogenesis and minimize uranium mobilization. The bioavailability of sorbed U(VI) was manipulated by addition of low-level carbonate (< 5 mM) followed by ethanol (1-1.5 mM). Addition of low levels of carbonate increased the concentration of aqueous U, indicating an increased rate of U desorption due to formation of uranyl carbonate complexes. Upon ethanol addition, aqueous U(VI) levels fell, indicating that the rate of microbial reduction exceeded the rate of desorption. Sulfate levels simultaneously decreased, with a corresponding increase in sulfide. When ethanol addition ended but carbonate addition continued, soluble U levels increased, indicating faster desorption than reduction. When bicarbonate addition stopped, aqueous U levels decreased, indicating adsorption to sediments. Changes in the sequence of carbonate and ethanol addition confirmed that carbonate-controlled desorption increased bioavailability of U(VI) for reduction.     

Mechanisms of strontium and uranium removal from high-level radioactive waste simulant solutions by the sorbent monosodium titanate

High-level waste (HLW) is a waste associated with the dissolution of spent nuclear fuel for the recovery of weapons-grade material. It is the priority problem for the U.S. Department of Energy's Environmental Management Program. Current HLW treatment processes at the Savannah River Site (Aiken, SC) include the use of monosodium titanate (MST, with a similar stoichiometry to NaTi2O5 x xH2O) to concentrate strontium (Sr) and actinides. The high affinity of MST for Sr and actinides in HLW solutions rich in Na+ is poorly understood. Mechanistic information about the nature of radionuclide uptake will provide insight about MST treatment reliability. Our study characterized the morphology of MST and the chemistry of sorbed Sr2+ and uranium [U(VI)] as uranyl ion, UO2(2+), on MST, which were added (individually) from stock solutions of Sr and 238U(VI) with spectroscopic and transmission electron microscopic techniques. The local structure of sorbed U varied with loading, but the local structure of Sr did not vary with loading. Sorbed Sr exhibited specific adsorption as partially hydrated species whereas sorbed U exhibited specific adsorption as monomeric and dimeric U(VI)-carbonate complexes. Sorption proved site specific. These differences in site specificity and sorption mechanism may account forthe difficulties associated with predicting Sr and U loading and removal kinetics using MST.     

Individual and competitive adsorption of arsenate and phosphate to a high-surface-area iron oxide-based sorbent

Individual and competitive adsorption of arsenate and phosphate were studied on a high-surface-area Fe/Mn-(hydr)oxide sorbent with surface and bulk properties similar to those of two-line ferrihydrite. It has maximum adsorption densities of 0.42 micromol As m(-2) at neutral pH and 1.24 micromol As m(-2) at pH 3. A surface complexation model (SCM) that used the diffuse double layer model was developed that could simulate single and binary sorbate adsorption over pH 4-9. The predominant adsorbed arsenate and phosphate species were modeled as bidentate binuclear surface complexes at low pH and as monodentate complexes at high pH. The model initially overpredicted the inhibition of arsenate adsorption by the presence of phosphate. The overprediction was resolved by separating surface sites into two types: ones to which both arsenate and phosphate bind and a smaller number to which only phosphate binds. The modified model predicted the competitive adsorption of arsenate and phosphate over pH 4-9 at total As concentrations of 6.67 and 80.1 microM and a total P concentration of 129 and 323 microM. The model may be used to predict arsenic adsorption to the sorbent for a given water source based on solution chemistry.     

Influence of calcite and dissolved calcium on uranium(VI) sorption to a hanford subsurface sediment

The influence of calcite and dissolved calcium on U(VI) adsorption was investigated using a calcite-containing sandy silt/clay sediment from the U. S. Department of Energy Hanford site. U(VI) adsorption to sediment, treated sediment, and sediment size fractions was studied in solutions that both had and had not been preequilibrated with calcite, at initial [U(VI)] = 10(-7)-10(-5) mol/L and final pH = 6.0-10.0. Kinetic and reversibility studies (pH 8.4) showed rapid sorption (30 min), with reasonable reversibility in the 3-day reaction time. Sorption from solutions equilibrated with calcite showed maximum U(VI) adsorption at pH 8.4 +/- 0.1. In contrast, calcium-free systems showed the greatest adsorption at pH 6.0-7.2. At pH > 8.4, U(VI) adsorption was identical from calcium-free and calcium-containing solutions. For calcite-presaturated systems, both speciation calculations and laser-induced fluorescence spectroscopic analyses indicated that aqueous U(VI) was increasingly dominated by Ca2UO2(CO3)3(0)(aq) at pH < 8.4 and thatformation of Ca2UO2(CO3)3(0)(aq) is what suppresses U(VI) adsorption. Above pH 8.4, aqueous U(VI) speciation was dominated by UO2(CO3)3(4-) in all solutions. Finally, results also showed that U(VI) adsorption was additive in regard to size fraction but not in regard to mineral mass: Carbonate minerals may have blocked U(VI) access to surfaces of higher sorption affinity.