Determining individual mineral contributions to U(VI) adsorption in a contaminated aquifer sediment: A fluorescence spectroscopy study

The adsorption and speciation of U(VI) was investigated on contaminated, fine grained sediment materials from the Hanford 300 area (SPP1 GWF) in simulated groundwater using cryogenic laser-induced U(VI) fluorescence spectroscopy combined with chemometric analysis. A series of reference minerals (montmorillonite, illite, Michigan chlorite, North Carolina chlorite, California clinochlore, quartz and synthetic 6-line ferrihydrite) was used for comparison that represents the mineralogical constituents of SPP1 GWF. Surface area-normalized K_d values were measured at U(VI) concentrations of 5 × 10⁻⁷ and 5 × 10⁻⁶ mol L⁻¹ that displayed the following affinity series: 6-line-ferrihydrite > North Carolina chlorite ≈ California clinochlore > quartz ≈ Michigan chlorite > illite > montmorillonite. Both time-resolved spectra and asynchronous two-dimensional (2D) correlation analysis of SPP1 GWF at different delay times indicated that two major adsorbed U(VI) species were present in the sediment that resembled U(VI) adsorbed on quartz and phyllosilicates. Simulations of the normalized fluorescence spectra confirmed that the speciation of SPP1 GWF was best represented by a linear combination of U(VI) adsorbed on quartz (90%) and phyllosilicates (10%). However, the fluorescence quantum yield for U(VI) adsorbed on phyllosilicates was lower than quartz and, consequently, its fractional contribution to speciation may be underestimated. Spectral comparison with literature data suggested that U(VI) exist primarily as inner-sphere complexes with surface silanol groups on quartz and as surface U(VI) tricarbonate complexes on phyllosilicates.     

Resupply mechanism to a contaminated aquifer: A laboratory study of U(VI) desorption from capillary fringe sediments

Contaminated capillary fringe sediments are believed to function as long-term source of U(VI) to Hanford’s 300 Area groundwater uranium plume that discharges to the Columbia River. The deep vadose zone at this site experiences seasonal water table elevation and water compositional changes in response to Columbia River stage. Batch and column desorption experiments of U(VI) were performed on two mildly contaminated sediments from this system that vary in hydrologic position to ascertain their U(VI) release behavior and factors controlling it. Solid phase characterization of the sediments was performed to identify mineralogic and chemical factors controlling U(VI) desorption. Low adsorbed U(VI) concentrations prevented spectroscopic analysis. The desorption behavior of U(VI) was different for the two sediments in spite of similar chemical and textural characteristics, and non-carbonate mineralogy. Adsorption strength and sorbed U(VI) lability was higher in the near-river sediment. The inland sediment displayed low sorbed U(VI) lability (∼10%) and measurable solid-phase carbonate content. Kinetic desorption was observed that was attributed to regeneration of labile U(VI) in the near river sediment, and carbonate mineral dissolution in the inland sediment. The desorption reaction was best described as an equilibrium surface complexation reaction. The noted differences in desorption behavior appear to result from U(VI) contamination and hydrologic history, as well as sediment carbonate content. Insights are provided on the dynamic adsorption/desorption behavior of contaminants in linked groundwater-river systems.     

The dissolution of synthetic Na-boltwoodite in sodium carbonate solutions

Uranyl silicates such as uranophane and Na-boltwoodite appear to control the solubility of uranium in certain contaminated sediments at the US Department of Energy Hanford site [Liu, C., Zachara, J.M., Qafoku, O., McKinley, J.P., Heald, S.M., Wang, Z. 2004. Dissolution of uranyl microprecipitates in subsurface sediments at Hanford Site, USA. Geochim. Cosmochim. Acta68, 4519-4537.]. Consequently, the solubility of synthetic Na-boltwoodite, Na(UO₂)(SiO₃OH) · 1.5H₂O, was determined over a wide range of bicarbonate concentrations, from circumneutral to alkaline pH, that are representative of porewater and groundwater compositions at the Hanford site and calcareous environments generally. Experiments were open to air. Results show that Na-boltwoodite dissolution was nearly congruent and its solubility and dissolution kinetics increased with increasing bicarbonate concentration and pH. A consistent set of solubility constants were determined from circumneutral pH (0 added bicarbonate) to alkaline pH (50 mM added bicarbonate). Average or 5.85 ± 0.0.26; using the Pitzer ion-interaction model or Davies equation, respectively. These values are close to the one determined by [Nguyen, S.N., Silva, R.J., Weed, H.C., Andrews, Jr., J.E., 1992. Standard Gibbs free energies of formation at the temperature 303.15 K of four uranyl silicates: soddyite, uranophane, sodium boltwoodite, and sodium weeksite. J. Chem. Thermodynamics24, 359-376.] under very different conditions (pH 4.5, Ar atmosphere).     

粤北下庄铀矿田中铀酰矿物的成分特征——对核废料处置库中UO2氧化行为的启示

下庄铀矿为一花岗岩型铀矿，矿田地处湿热气候条件下，沥青铀矿普遍产于破碎带中，这种特定的产出环境致使该区沥青铀矿经受了强烈的风化，形成种类繁多、数量丰富的铀酰矿物；而我国高放废物地质处置库拟建在花岗岩体中。因此，下庄铀矿田是开展核废料氧化的天然类比研究的理想地区，并对我国的高放废物地质处置库的安全性评价有重要的指导作用。下庄铀矿田的铀酰矿物组合为铀酰氢氧化物、铀酰硅酸盐和铀酰磷酸盐，包括柱铀矿、黄钙铀矿、calciouranoite、红铀矿、富硅铀酰相、硅钙铀矿、钙铀云母和盈江铀矿等。根据它们的空间分布特征可划分成两个风化系列，即硅酸盐风化系列和磷酸盐风化系列，其共生次序分别为：沥青铀矿→铀酰氢氧化物（氧化物）→富硅铀酰相→硅钙铀矿和沥青铀矿→铀酰氢氧化物（氧化物）→钙铀云母→盈江铀矿。在该矿田中，铀酰氢氧化物是亚稳定相矿物，常常被铀酰硅酸盐或磷酸盐取代，因此，铀酰氢氧化物仅出现在少数样品中，而铀酰硅酸盐和铀酰磷酸盐矿物则非常普遍。矿田中的铀酰矿物在化学成分上以富钙为其显著特征，由于核废料地质处置库近场地下水中的Ca^2＋含量应该明显比下庄矿田地下水中的高，因此，我们预测含Ca的铀酰硅酸盐和铀酰磷酸盐矿物等热力学上的稳定物相很可能是地质处置系统中最主要的铀酰矿物，处置库内放射性核素的迁移主要是由这些矿物控制的。     

Approaches to surface complexation modeling of Uranium(VI) adsorption on aquifer sediments

Uranium(VI) adsorption onto aquifer sediments was studied in batch experiments as a function of pH and U(VI) and dissolved carbonate concentrations in artificial groundwater solutions. The sediments were collected from an alluvial aquifer at a location upgradient of contamination from a former uranium mill operation at Naturita, Colorado (USA). The ranges of aqueous chemical conditions used in the U(VI) adsorption experiments (pH 6.9 to 7.9; U(VI) concentration 2.5 · 10⁻⁸ to 1 · 10⁻⁵ M; partial pressure of carbon dioxide gas 0.05 to 6.8%) were based on the spatial variation in chemical conditions observed in 1999-2000 in the Naturita alluvial aquifer. The major minerals in the sediments were quartz, feldspars, and calcite, with minor amounts of magnetite and clay minerals. Quartz grains commonly exhibited coatings that were greater than 10 nm in thickness and composed of an illite-smectite clay with occluded ferrihydrite and goethite nanoparticles. Chemical extractions of quartz grains removed from the sediments were used to estimate the masses of iron and aluminum present in the coatings. Various surface complexation modeling approaches were compared in terms of the ability to describe the U(VI) experimental data and the data requirements for model application to the sediments. Published models for U(VI) adsorption on reference minerals were applied to predict U(VI) adsorption based on assumptions about the sediment surface composition and physical properties (e.g., surface area and electrical double layer). Predictions from these models were highly variable, with results overpredicting or underpredicting the experimental data, depending on the assumptions used to apply the model. Although the models for reference minerals are supported by detailed experimental studies (and in ideal cases, surface spectroscopy), the results suggest that errors are caused in applying the models directly to the sediments by uncertain knowledge of: 1) the proportion and types of surface functional groups available for adsorption in the surface coatings; 2) the electric field at the mineral-water interface; and 3) surface reactions of major ions in the aqueous phase, such as Ca²⁺, Mg²⁺, HCO₃⁻, SO₄²⁻, H₄SiO₄, and organic acids. In contrast, a semi-empirical surface complexation modeling approach can be used to describe the U(VI) experimental data more precisely as a function of aqueous chemical conditions. This approach is useful as a tool to describe the variation in U(VI) retardation as a function of chemical conditions in field-scale reactive transport simulations, and the approach can be used at other field sites. However, the semi-empirical approach is limited by the site-specific nature of the model parameters.     

The effects of uranium speciation on the rate of U(VI) reduction by Shewanella oneidensis MR-1

We measured the kinetics of U(VI) reduction by Shewanella oneidensis MR-1 under anaerobic conditions in the presence of variable concentrations of either EDTA or dissolved Ca. We measured both total dissolved U and U(VI) concentrations in solution as a function of time. In separate experiments, we also measured the extent of U(VI) adsorption onto S. oneidensis in order to quantify the thermodynamic stabilities of the important U(VI)-bacterial surface complexes. In the EDTA experiments, the rate of U(IV) production increased with increasing EDTA concentration. However, the total dissolved U concentrations remained constant and identical to the initial U concentrations during the course of the experiments for all EDTA-bearing systems. Additionally, the U(VI) reduction rate in the EDTA experiments exhibited a strong correlation to the concentration of the aqueous U⁴⁺-EDTA complex. We conclude that the U(VI) reduction rate increases with increasing EDTA concentration, likely due to U⁴⁺-EDTA aqueous complexation which removes U(IV) from the cell surface and prevents UO₂ precipitation.In the Ca experiments, the U(VI) reduction rate decreased as Ca concentration increased. Our thermodynamic modeling results based on the U(VI) adsorption data demonstrate that U(VI) was adsorbed onto the bacterial surface in the form of a Ca-uranyl-carbonate complex in addition to a number of other Ca-free uranyl complexes. The observed U(VI) reduction rates in the presence of Ca exhibit a strong negative correlation to the concentration of the Ca-uranyl-carbonate bacterial surface complex, but a strong positive correlation to the total concentration of all the other Ca-free uranyl surface complexes. Thus, the concentration of these Ca-free uranyl surface complexes appears to control the rate of U(VI) reduction by S. oneidensis in the presence of dissolved Ca. Our results demonstrate that U speciation, both of U(VI) before reduction and of U(IV) after reduction, affects the reduction kinetics, and that thermodynamic modeling of the U speciation may be useful in the prediction of reduction kinetics in realistic geologic settings.     

Products of abiotic U(VI) reduction by biogenic magnetite and vivianite

Reductive immobilization of uranium by the stimulation of dissimilatory metal-reducing bacteria (DMRB) has been investigated as a remediation strategy for subsurface U(VI) contamination. In those environments, DMRB may utilize a variety of electron acceptors, such as ferric iron which can lead to the formation of reactive biogenic Fe(II) phases. These biogenic phases could potentially mediate abiotic U(VI) reduction. In this work, the DMRB Shewanella putrefaciens strain CN32 was used to synthesize two biogenic Fe(II)-bearing minerals: magnetite (a mixed Fe(II)-Fe(III) oxide) and vivianite (an Fe(II)-phosphate). Analysis of abiotic redox interactions between these biogenic minerals and U(VI) showed that both biogenic minerals reduced U(VI) completely. XAS analysis indicates significant differences in speciation of the reduced uranium after reaction with the two biogenic Fe(II)-bearing minerals. While biogenic magnetite favored the formation of structurally ordered, crystalline UO₂, biogenic vivianite led to the formation of a monomeric U(IV) species lacking U-U associations in the corresponding EXAFS spectrum. To investigate the role of phosphate in the formation of monomeric U(IV) such as sorbed U(IV) species complexed by mineral surfaces, versus a U(IV) mineral, uranium was reduced by biogenic magnetite that was pre-sorbed with phosphate. XAS analysis of this sample also revealed the formation of monomeric U(IV) species suggesting that the presence of phosphate hinders formation of UO₂. This work shows that U(VI) reduction products formed during in situ biostimulation can be influenced by the mineralogical and geochemical composition of the surrounding environment, as well as by the interfacial solute-solid chemistry of the solid-phase reductant.     

Reactions of the feldspar surface with metal ions: Sorption of Pb(II), U(VI) and Np(V), and surface analytical studies of reaction with Pb(II) and U(VI)

Feldspar minerals are thermodynamically unstable in the near-surface environment and their surfaces are well known to react readily with aqueous solutions, leading to incongruent dissolution at low pH values, but congruent dissolution at neutral and high pH values. Interactions with mineral surfaces are an important control on the environmental transport of trace elements and detrital feldspars are abundant in soils and sediments. However, the interactions of metal ions in solution with the reacting feldspar surface have not been widely explored. The interactions of Pb(II), U(VI) and Np(V) ions with the feldspar surface have therefore been studied. Lead is taken up by the microcline surface at pH 6 and 10, but no uptake could be measured at pH 2. There was measurable uptake of Pb(II) on the plagioclase surface at pH 2, 6 and 10. Uptake always increased with pH. In most conditions, Pb(II) reacts through cation exchange process although, at high pH, a discrete phase, probably hydrocerrusite, is observed by atomic force microscopy (AFM) to precipitate on the plagioclase surface. Supersaturation with hydrocerrusite in these conditions is expected from thermodynamic calculations. Uptake of uranyl ion , generally through surface complex formation, could only be measured at pH 6 and 10. At pH 6 and an initial U(VI) concentration above 21.0 μM, precipitation of becquerelite (Ca[(UO₂)₃O₂(OH)₃]₂·8H₂O), identified by AFM and characterised by grazing incidence X-ray diffraction and X-ray photoelectron spectroscopy, is observed on plagioclase. The U(VI) concentration range in which becquerelite precipitation begins (dissolved U(VI) 1-5 μM) is consistent with that predicted from thermodynamic modelling. On plagioclase feldspar, secondary ion mass spectrometry showed diffusion of uranium into the altered surface layer. Uptake of the neptunyl ion (Np(V)) was found at pH 6 and 10 for microcline and at pH 2, 6 and 10 for plagioclase, and was generally lower than uptake of U(VI). By combining batch sorption experiments with imaging and surface analysis, and thermodynamic modelling, it has been possible to gain a mechanistic insight into the reactions of the feldspar surface with metal ions in solution.     

Evidence for multiple modes of uranium immobilization by an anaerobic bacterium

Microbial reduction of hexavalent uranium has been studied widely for its potential role in bioremediation and immobilization of soluble U(VI) in contaminated groundwater. More recently, some microorganisms have been examined for their role in immobilization of U(VI) via precipitation of uranyl phosphate minerals mediated by microbial phosphate release, alleviating the requirement for long-term redox control. Here, we investigated the mechanism of U(VI) removal mediated by an environmental isolate, strain UFO1, that is indigenous to the Field Research Center (FRC) in Oak Ridge, TN and has been detected in U(VI)-contaminated sediments. Changes in U(VI) speciation were examined in the presence and absence of the electron-shuttling moiety, anthraquinone-2,6-disulfonate (AQDS). Cell suspensions were capable of nearly complete removal of 100 μM U(VI) from solution within 48 h; U(VI) removal was not dependent on the presence of an exogenous electron donor or AQDS, although AQDS increased the rate of U(VI) removal. X-ray Absorption Near Edge Structure (XANES) and Extended X-ray Absorption Fine Structure (EXAFS) spectroscopic measurements indicated that U(IV) was the predominant oxidation state of uranium in cell suspensions in both the absence and presence of 100 μM AQDS. Interestingly, 17% of the cell-associated precipitates in a U(VI)-treated suspension that lacked AQDS had spectral characteristics consistent with a uranyl phosphate solid phase. The potential involvement of phosphate was consistent with observed increases in soluble phosphate concentrations over time in UFO1 cell suspensions, which suggested phosphate liberation from the cells. TEM-EDS confirmed the presence of uranyl phosphate with a U:P ratio consistent with autunite (1:1). EXAFS analyses further suggested that U(IV) was bound to low-Z neighbors such as C or P, inferred to be present as functional groups on biomass. These results suggest that strain UFO1 has the ability to facilitate U(VI) removal from solution via reductive and phosphate precipitation mechanisms. Both mechanisms offer potential for the remediation of U-contaminated sediments at the FRC or elsewhere.     

Uranium(VI) sorption on iron oxides in Hanford Site sediment: Application of a surface complexation model

Sorption of U(VI) on Hanford fine sand (HFS) with varying Fe-oxide (especially ferrihydrite) contents showed that U(VI) sorption increased with the incremental addition of synthetic ferrihydrite into HFS, consistent with ferrihydrite being one of the most reactive U(VI) sorbents present in natural sediments. Surface complexation model (SCM) calculations for U(VI) sorption, using only U(VI) surface-reaction constants obtained from U(VI) sorption data on freshly synthesized ferrihydrite at different pHs, were similar to the measured U(VI) sorption results on pure synthetic ferrihydrite and on HFS with high contents of ferrihydrite (5 wt%) added. However, the SCM prediction using only U(VI) sorption reactions and constants for synthetic ferrihydrite overestimated U(VI) sorption on the natural HFS or HFS with addition of low amounts of added ferrihydrite (1 wt% added). Over-predicted U(VI) sorption was attributed to reduced reactivity of natural ferrihydrite present in Hanford Site sediments, compared to freshly prepared synthetic ferrihydrite. Even though the SCM general composite (GC) approach is considered to be a semi-quantitative estimation technique for contaminant sorption, which requires systematic experimental data on the sorbent–sorbate system being studied to obtain credible SCM parameters, the general composite SCM model was still found to be a useful technique for describing U(VI) sorption on natural sediments. Based on U(VI) batch sorption results, two simple U(VI) monodentate surface species, SO_UO₂HCO₃ and SO_UO₂OH on ferrihydrite and phyllosillicate in HFS, respectively, can be successfully used to describe U(VI) sorption onto Hanford Site sediment contacting varying geochemical solutions.     

Site-specific incorporation of uranyl carbonate species at the calcite surface

Spatially resolved luminescence spectra from U(VI) co-precipitated at the (101?4) growth surface of synthetic calcite single crystals confirm heterogeneous incorporation corresponding to the distribution of structurally non-equivalent steps composing the vicinal surfaces of spiral growth hillocks. Spectral structure from U(VI) luminescence at the “-” vicinal regions and featureless, weak luminescence at the “+” vicinal regions are consistent with previously reported observations of enrichment at the former sites during calcite growth. Luminescence spectra differ between the non-equivalent regions of the crystal, with the spectral features from the “-” vicinal region corresponding to those observed in bulk calcite samples. Subtle spectral shifts are observed from U(VI) co-precipitated with microcrystalline calcite synthesized by a different method, and all of the U(VI)-calcite sample spectra differ significantly from that of U(VI) co-precipitated with aragonite.The step-selective incorporation of U(VI) can be explained by a proposed model in which the allowed orientation for adsorption of the dominant calcium uranyl triscarbonate species is controlled by the atomic arrangement at step edges. Differences in the tilt angles of carbonate groups between non-equivalent growth steps favor adsorption of the calcium uranyl triscarbonate species at “-” steps, as observed in experiments.     

Uranyl adsorption onto montmorillonite: Evaluation of binding sites and carbonate complexation

The fate and transport of uranium in contaminated soils and sediments may be affected by adsorption onto the surface of minerals such as montmorillonite. Extended X-ray absorption fine structure (EXAFS) spectroscopy has been used to investigate the adsorption of uranyl (UO₂²⁺) onto Wyoming montmorillonite. At low pH (∼4) and low ionic strength (10⁻³ M), uranyl has an EXAFS spectrum indistinguishable from the aqueous uranyl cation, indicating binding via cation exchange. At near-neutral pH (∼7) and high ionic strength (1 M), the equatorial oxygen shell of uranyl is split, indicating inner-sphere binding to edge sites. Linear-combination fitting of the spectra of samples reacted under conditions where both types of binding are possible reveals that cation exchange at low ionic strengths on SWy-2 may be more important than predicted by past surface complexation models of U(VI) adsorption on related montmorillonites. Analysis of the binding site on the edges of montmorillonite suggests that U(VI) sorbs preferentially to [Fe(O,OH)₆] octahedral sites over [Al(O,OH)₆] sites. When bound to edge sites, U(VI) occurs as uranyl-carbonato ternary surface complexes in systems equilibrated with atmospheric CO₂. Polymeric surface complexes were not observed under any of the conditions studied. Current surface complexation models of uranyl sorption on clay minerals may need to be reevaluated to account for the possible increased importance of cation exchange reactions at low ionic strengths, the presence of reactive octahedral iron surface sites, and the formation of uranyl-carbonato ternary surface complexes. Considering the adsorption mechanisms observed in this study, future studies of U(VI) transport in the environment should consider how uranium retardation will be affected by changes in key solution parameters, such as pH, ionic strength, exchangeable cation composition, and the presence or absence of CO₂.     

Dissolution of uranyl microprecipitates in subsurface sediments at Hanford Site, USA

The dissolution of uranium was investigated from contaminated sediments obtained at the US. Department of Energy (U.S. DOE) Hanford site. The uranium existed in the sediments as uranyl silicate microprecipitates in fractures, cleavages, and cavities within sediment grains. Uranium dissolution was studied in Na, Na-Ca, and NH₄ electrolytes with pH ranging from 7.0 to 9.5 under ambient CO₂ pressure. The rate and extent of uranium dissolution was influenced by uranyl mineral solubility, carbonate concentration, and mass transfer rate from intraparticle regions. Dissolved uranium concentration reached constant values within a month in electrolytes below pH 8.2, whereas concentrations continued to rise for over 200 d at pH 9.0 and above. The steady-state concentrations were consistent with the solubility of Na-boltwoodite and/or uranophane, which exhibit similar solubility under the experimental conditions. The uranium dissolution rate increased with increasing carbonate concentration, and was initially fast. It decreased with time as solubility equilibrium was attained, or dissolution kinetics or mass transfer rate from intraparticle regions became rate-limiting. Microscopic observations indicated that uranium precipitates were distributed in intragrain microfractures with variable sizes and connectivity to particle surfaces. Laser-induced fluorescence spectroscopic change of the uranyl microprecipitates was negligible during the long-term equilibration, indicating that uranyl speciation was not changed by dissolution. A kinetic model that incorporated mineral dissolution kinetics and grain-scale, fracture-matrix diffusion was developed to describe uranium release rate from the sediment. Model calculations indicated that 50-95% of the precipitated uranium was associated with fractures that were in close contact with the aqueous phase. The remainder of the uranium was deeply imbedded in particle interiors and exhibited effective diffusivities that were over three orders of magnitude lower than those in the fractures.     

The effect of U(VI) bioreduction kinetics on subsequent reoxidation of biogenic U(IV)

Microbially mediated in situ reduction of soluble U(VI) to insoluble U(IV) (as UO₂) has been proposed as a means of preventing the migration of that radionuclide with groundwater, but preventing the oxidative resolubilization of U has proven difficult. We hypothesized that relatively slow rates of U(VI) bioreduction would yield larger UO₂ precipitates that would be more resistant to oxidation than those produced by rapid U(VI) bioreduction. We manipulated U(VI) bioreduction rates by varying the density of Shewanella putrefaciens CN32 added to U(VI) containing solutions with lactate as an electron donor. Characterization of biogenic UO₂ particles by extended X-ray absorption fine-structure spectroscopy and transmission electron microscopy revealed that UO₂ nanoparticles formed by relatively slow rates of U(VI) reduction were larger and more highly aggregated than those formed by relatively rapid U(VI) reduction. UO₂ particles formed at various rates were incubated under a variety of abiotically and biologically oxidizing conditions. In all cases, UO₂ that was formed by relatively slow U(VI) reduction was oxidized at a slower rate and to a lesser extent than UO₂ formed by relatively rapid U(VI) bioreduction, suggesting that the stability of UO₂ in situ may be enhanced by stimulation of relatively slow rates of U(VI) reduction.     

The effect of Si and Al concentrations on the removal of U(VI) in the alkaline conditions created by NH3 gas

Remediation of uranium in the deep unsaturated zone is a challenging task, especially in the presence of oxygenated, high-carbonate alkalinity soil and pore water composition typical for arid and semi-arid environments of the western regions of the U.S. This study evaluates the effect of various pore water constituencies on changes of uranium concentrations in alkaline conditions, created in the presence of reactive gases such as NH₃ to effectively mitigate uranium contamination in the vadose zone sediments. This contaminant is a potential source for groundwater pollution through slow infiltration of soluble and highly mobile uranium species towards the water table. The objective of this research was to evaluate uranium sequestration efficiencies in the alkaline synthetic pore water solutions prepared in a broad range of Si, Al, and bicarbonate concentrations typically present in field systems of the western U.S. regions and identify solid uranium-bearing phases that result from ammonia gas treatment. In previous studies (Szecsody et al. 2012; Zhong et al. 2015), although uranium mobility was greatly decreased, solid phases could not be identified at the low uranium concentrations in field-contaminated sediments. The chemical composition of the synthetic pore water used in the experiments varied for silica (5–250 mM), Al³⁺ (2.8 or 5 mM), HCO₃⁻ (0–100 mM) and U(VI) (0.0021–0.0084 mM) in the solution mixture. Experiment results suggested that solutions with Si concentrations higher than 50 mM exhibited greater removal efficiencies of U(VI). Solutions with higher concentrations of bicarbonate also exhibited greater removal efficiencies for Si, Al, and U(VI). Overall, the silica polymerization reaction leading to the formation of Si gel correlated with the removal of U(VI), Si, and Al from the solution. If no Si polymerization was observed, there was no U removal from the supernatant solution. Speciation modeling indicated that the dominant uranium species in the presence of bicarbonate were anionic uranyl carbonate complexes (UO₂(CO₃)₂⁻² and UO₂(CO₃)₃⁻⁴) and in the absence of bicarbonate in the solution, U(VI) major species appeared as uranyl-hydroxide (UO₂(OH)₃⁻ and UO₂(OH)₄⁻²) species. The model also predicted the formation of uranium solid phases. Uranyl carbonates as rutherfordine [UO₂CO₃], cejkaite [Na₄(UO2)(CO₃)₃] and hydrated uranyl silicate phases as Na-boltwoodite [Na(UO₂)(SiO₄)·1.5H₂O] were anticipated for most of the synthetic pore water compositions amended from medium (2.9 mM) to high (100 mM) bicarbonate concentrations.     

Enhanced microbial reduction of Cr(VI) and U(VI) by different natural organic matter fractions

Although direct microbial reduction of Cr(VI) and U(VI) is known, few studies have examined the kinetics and the underlying mechanisms of the reduction of these contaminants by different natural organic matter (NOM) fractions in the presence or absence of microorganisms. In this study, NOM was found to chemically reduce Cr(VI) at pH 3, but the reduction rates were negligible at pH ∼7. The abiotic reduction of U(VI) by NOM was not observed, possibly because of the presence of small amounts of nitrate in the reactant solution. However, all NOM fractions, particularly the soil humic acid (HA), enhanced the bioreduction of Cr(VI) or U(VI) in the presence of Shewanella putrefaciens CN32. The reduction rates varied greatly among NOM fractions with different chemical and structural properties: the polyphenolic-rich NOM-PP fraction appeared to be the most reactive in abiotically reducing Cr(VI) at a low pH, but soil HA was more effective in mediating the microbial reduction of Cr(VI) and U(VI) under anaerobic, circumneutral pH conditions. These observations are attributed to an increased solubility and conformational changes of the soil HA with pH and, more importantly, its relatively high contents of polycondensed and conjugated aromatic organic moieties. An important implication of this study is that, depending on chemical and structural properties, different NOM components may play different roles in enhancing the bioreduction of Cr(VI) and U(VI) by microorganisms. Polycondensed aromatic humic materials may be particularly useful in mediating the bioreduction and rapid immobilization of these contaminant metals in soil.     

Equilibrium and kinetic aspects of soddyite dissolution and secondary phase precipitation in aqueous suspension

The dissolution and transformation of soddyite ([UO₂]₂SiO₄ · 2H₂O) have been examined in aqueous suspension at pH 6 and 0.01 M NaNO₃. Soddyite is an important component of the paragenetic sequence of secondary minerals that arises from the weathering of uraninite ore deposits and corrosion of spent nuclear fuel. A soddyite of high purity and crystallinity was synthesized in the laboratory for use in dissolution experiments. In batch experiments, rapid dissolution occurred over an initial period of several hours followed by continuing steady-state dissolution for up to 700 h. Up to 200 h, U and Si were released into solution at their stoichiometric 2:1 ratio in soddyite. A decrease in the dissolved U concentration was observed at longer times, indicating the precipitation of a new phase. Even after precipitation of the secondary phase, the continuing dissolution of soddyite could be inferred from increasing dissolved Si concentrations. Through the use of X-ray diffraction, Raman spectroscopy, and scanning electron microscopy, the precipitated phase was identified as a clarkeite-like sodium uranyl oxide hydrate. The sodium uranyl oxide hydrate was ultimately the solubility-controlling solid, despite being only a minor component. Soddyite dissolution rates were quantified in flow-through experiments, in which reaction products were flushed from the reactors, thereby avoiding reprecipitation of U. The measured dissolution rate at pH 6 was 0.71 μmol U m⁻² h⁻¹. A slower dissolution rate of 0.44 μmol U m⁻² h⁻¹ was observed when 100 μM dissolved Si was added to the reactor influent.     

A comparative study of the effect of desferrioxamine B, oxalic acid, and Na-alginate on the desorption of U(VI) from goethite at pH 6 and 25 °C

Organic ligands affect the sorption and mobility of radionuclides in soils. Batch desorption experiments on goethite particles reveal the extent of uranyl desorption and hence bioavailability with different organic acids. The desorptive strength increases in the following order: background electrolyte < Na-alginate < desferrioxamine B (DFO-B) < oxalate. The sequence is consistent with decreasing molecular size and mass from alginate via DFO-B to oxalate. The concomitant Fe release in the desorption experiments indicates that desorption from goethite and not dissolution of goethite governs the mobility of adsorbed U(VI). A compilation of DFO-B surface excesses on goethite from our experiments together with literature values indicate that DFO-B adsorbs at a constant ∼3% to the goethite surface. It is surprising that such a small fraction suffices to account for the considerable uranyl desorption and thus remobilization of a radionuclide into solution. Oxalate displays higher surface concentrations but still lower than the determined uranyl surface excess. It follows that based on the high U(VI) stability constants, both organic ligands induce the desorption of uranyl species by increasing the chemical affinity of the aqueous phase. In the case of alginate, desorption of uranyl is weak and adsorbed alginate hampers any considerable detachment of U(VI) in the presence of the more potent ligands, DFO-B and oxalate. This inhibition is based on biosorption and in this respect polysaccharides in soils may retard and even halt the advance of actinides through the soil column. This hypothesis calls for further studies into the interaction of siderophores and polysaccharides with soil adsorbents and their role in the mobilization of contaminant metals.     

The effect of pH and natural microbial phosphatase activity on the speciation of uranium in subsurface soils

The biomineralization of U(VI) phosphate as a result of microbial phosphatase activity is a promising new bioremediation approach to immobilize uranium in both aerobic and anaerobic conditions. In contrast to reduced uranium minerals such as uraninite, uranium phosphate precipitates are not susceptible to changes in oxidation conditions and may represent a long-term sink for uranium in contaminated environments. So far, the biomineralization of U(VI) phosphate has been demonstrated with pure cultures only. In this study, two uranium contaminated soils from the Department of Energy Oak Ridge Field Research Center (ORFRC) were amended with glycerol phosphate as model organophosphate source in small flow-through columns under aerobic conditions to determine whether natural phosphatase activity of indigenous soil bacteria was able to promote the precipitation of uranium(VI) at pH 5.5 and 7.0. High concentrations of phosphate (1-3 mM) were detected in the effluent of these columns at both pH compared to control columns amended with U(VI) only, suggesting that phosphatase-liberating microorganisms were readily stimulated by the organophosphate substrate. Net phosphate production rates were higher in the low pH soil (0.73 ± 0.17 mM d⁻¹) compared to the circumneutral pH soil (0.43 ± 0.31 mM d⁻¹), suggesting that non-specific acid phosphatase activity was expressed constitutively in these soils. A sequential solid-phase extraction scheme and X-ray absorption spectroscopy measurements were combined to demonstrate that U(VI) was primarily precipitated as uranyl phosphate minerals at low pH, whereas it was mainly adsorbed to iron oxides and partially precipitated as uranyl phosphate at circumneutral pH. These findings suggest that, in the presence of organophosphates, microbial phosphatase activity can contribute to uranium immobilization in both low and circumneutral pH soils through the formation of stable uranyl phosphate minerals.     

Adsorption of Fe(II) and U(VI) to carboxyl-functionalized microspheres: The influence of speciation on uranyl reduction studied by titration and XAFS

The chemical reduction of U(VI) by Fe(II) is a potentially important pathway for immobilization of uranium in subsurface environments. Although the presence of surfaces has been shown to catalyze the reaction between Fe(II) and U(VI) aqueous species, the mechanism(s) responsible for the enhanced reactivity remain ambiguous. To gain further insight into the U-Fe redox process at a complexing, non-conducting surface that is relevant to common organic phases in the environment, we studied suspensions containing combinations of 0.1 mM U(VI), 1.0 mM Fe(II), and 4.2 g/L carboxyl-functionalized polystyrene microspheres. Acid-base titrations were used to monitor protolytic reactions, and Fe K-edge and U L-edge X-ray absorption fine structure spectroscopy was used to determine the valence and atomic environment of the adsorbed Fe and U species. In the Fe + surface carboxyl system, a transition from monomeric to oligomeric Fe(II) surface species was observed between pH 7.5 and pH 8.4. In the U + surface carboxyl system, the U(VI) cation was adsorbed as a mononuclear uranyl-carboxyl complex at both pH 7.5 and 8.4. In the ternary U + Fe + surface carboxyl system, U(VI) was not reduced by the solvated or adsorbed Fe(II) at pH 7.5 over a 4-month period, whereas complete and rapid reduction to U(IV) nanoparticles occurred at pH 8.4. The U(IV) product reoxidized rapidly upon exposure to air, but it was stable over a 4-month period under anoxic conditions. Fe atoms were found in the local environment of the reduced U(IV) atoms at a distance of 3.56 Å. The U(IV)-Fe coordination is consistent with an inner-sphere electron transfer mechanism between the redox centers and involvement of Fe(II) atoms in both steps of the reduction from U(VI) to U(IV). The inability of Fe(II) to reduce U(VI) in solution and at pH 7.5 in the U + Fe + carboxyl system is explained by the formation of a transient, “dead-end” U(V)-Fe(III) complex that blocks the U(V) disproportionation pathway after the first electron transfer. The increased reactivity at pH 8.4 relative to pH 7.5 is explained by the reaction of U(VI) with an Fe(II) oligomer, whereby the bonds between Fe atoms facilitate the transfer of a second electron to the hypothetical U(V)-Fe(III) intermediate. We discuss how this mechanism may explain the commonly observed higher efficiency of uranyl reduction by adsorbed or structural Fe(II) relative to aqueous Fe(II).