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1.
Recent studies of uranium(VI) geochemistry have focused on the potentially important role of the aqueous species, CaUO2(CO3)32− and Ca2UO2(CO3)30(aq), on inhibition of microbial reduction and uranium(VI) aqueous speciation in contaminated groundwater. However, to our knowledge, there have been no direct studies of the effects of these species on U(VI) adsorption by mineral phases. The sorption of U(VI) on quartz and ferrihydrite was investigated in NaNO3 solutions equilibrated with either ambient air (430 ppm CO2) or 2% CO2 in the presence of 0, 1.8, or 8.9 mM Ca2+. Under conditions where the Ca2UO2(CO3)30(aq) species predominates U(VI) aqueous speciation, the presence of Ca in solution lowered U(VI) adsorption on quartz from 77% in the absence of Ca to 42% and 10% at Ca concentrations of 1.8 and 8.9 mM, respectively. U(VI) adsorption to ferrihydrite decreased from 83% in the absence of Ca to 57% in the presence of 1.8 mM Ca. Surface complexation model predictions that included the formation constant for aqueous Ca2UO2(CO3)30(aq) accurately simulated the effect of Ca2+ on U(VI) sorption onto quartz and ferrihydrite within the thermodynamic uncertainty of the stability constant value. This study confirms that Ca2+ can have a significant impact on the aqueous speciation of U(VI), and consequently, on the sorption and mobility of U(VI) in aquifers.  相似文献   

2.
A mixing of metal-loaded acid mine drainage with shallow groundwater or surface waters usually initiates oxidation and/or hydrolysis of dissolved metals such as iron (Fe) and aluminum (Al). Colloidal particles may appear and agglomerate with increasing pH. Likewise chemical conditions may occur while flooding abandoned uranium mines. Here, the risk assessment of hazards requires reliable knowledge on the mobility of uranium (U). A flooding process was simulated at mesocosm scale by mixing U-contaminated acid mine water with near-neutral groundwater under oxic conditions. The mechanism of U-uptake by fresh precipitates and the molecular structure of U bonding were determined to estimate the mobility of U(VI). Analytical and spectroscopic methods such as Extended X-ray Absorption Fine-Structure (EXAFS) spectroscopy at the Fe K-edge and the U LIII-edge, and Attenuated Total Reflectance Fourier Transform Infrared (ATR-FTIR) spectroscopy were employed. The freshly formed precipitate was identified as colloidal two-line ferrihydrite. It removed U(VI) from solution by sorption processes, while surface precipitation or structural incorporation of U was not observed. EXAFS data suggest a mononuclear inner-sphere, edge-sharing complex of U(VI) with ferrihydrite in the absence of dissolved carbonate. By employing a novel EXAFS analysis method, Monte Carlo Target Transformation Factor Analysis, we could for the first time ascertain a 3-D configuration of this sorption complex without the necessity to invoke formation of a ternary complex. The configuration suggests a slightly tilted position of the adsorbed unit relative to the edge-sharing Fe(O, OH)6 octahedra. In the presence of dissolved carbonate and at pH ∼8.0, a distal carbonate O-atom at ∼4.3 Å supports formation of ternary U(VI)-carbonato surface complexes. The occurrence of these complexes was also confirmed by ATR-FTIR. However, in slightly acidic conditions (pH 5-6) in equilibrium with atmospheric CO2, the U(VI) sorption on ferrihydrite was dominated by the binary complex species Fe(O)2UO2, whereas ternary U(VI)-carbonato surface complexes were of minor relevance. While sulfate and silicate were also present in the mine water, they had no detectable influence on U(VI) surface complexation. Our experiments demonstrate that U(VI) forms stable inner-sphere sorption complexes even in the presence of carbonate and at slightly alkaline pH, conditions which previously have been assumed to greatly accelerate the mobility of U(VI) in aqueous environments. Depending on the concentrations of U(VI) and carbonate, the type of surface complexes may change from binary uranyl-ferrihydrite to ternary carbonato-uranyl-ferrihydrite complexes. These different binding mechanisms are likely to influence the binding stability and retention of U(VI) at the macroscopic level.  相似文献   

3.
The potential health impact of As in drinking water supply systems in the Mississippi River Valley alluvial aquifer in the state of Arkansas, USA is significant. In this context it is important to understand the occurrence, distribution and mobilization of As in the Mississippi River Valley alluvial aquifer. Application of surface complexation models (SCMs) to predict the sorption behavior of As and hydrous Fe oxides (HFO) in the laboratory has increased in the last decade. However, the application of SCMs to predict the sorption of As in natural sediments has not often been reported, and such applications are greatly constrained by the lack of site-specific model parameters. Attempts have been made to use SCMs considering a component additivity (CA) approach which accounts for relative abundances of pure phases in natural sediments, followed by the addition of SCM parameters individually for each phase. Although few reliable and internally consistent sorption databases related to HFO exist, the use of SCMs using laboratory-derived sorption databases to predict the mobility of As in natural sediments has increased. This study is an attempt to evaluate the ability of the SCMs using the geochemical code PHREEQC to predict solid phase As in the sediments of the Mississippi River Valley alluvial aquifer in Arkansas. The SCM option of the double-layer model (DLM) was simulated using ferrihydrite and goethite as sorbents quantified from chemical extractions, calculated surface-site densities, published surface properties, and published laboratory-derived sorption constants for the sorbents. The model results are satisfactory for shallow wells (10.6 m below ground surface), where the redox condition is relatively oxic or mildly suboxic. However, for the deep alluvial aquifer (21-36.6 m below ground surface) where the redox condition is suboxic to anoxic, the model results are unsatisfactory.  相似文献   

4.
Cellulosic materials, such as wood, paper products and cardboard that have been co-disposed with low-level nuclear waste have been shown to produce leachate with natural organic matter (NOM) concentrations of hundreds of mg/L C and, as such, have the potential to influence the fate and transport of radionuclides in the subsurface environment. The objective of this study was to examine the influence of NOM on the sorption of Eu (an analogue for trivalent radionuclides) to two coastal plain sediments from the US Department of Energy’s Savannah River Site. Particular attention was directed at quantifying Eu interactions with NOM sorbed to sediments (NOMsed) in laboratory experiments and developing conditional stability constants for that interaction using the thermodynamic equilibrium speciation model MINTEQA2. Europium sorption to the two sediments systematically increased as pH increased from 3.9 to 6.7. With increasing additions of NOM to the aqueous phase from 0 to 222 mg/L C, Eu sorption initially increased to a maximum at 10 mg/L C NOMaq and then decreased with increasing NOMaq concentrations. Increases in Eu sorption at low NOM additions was attributed to the sorption of NOM to the sediment surface increasing the number of sorption sites on the low cation-exchange capacity sediments and/or increasing the association constant (log K) for the Eu-sediment surface reaction. Decreases in Eu sorption at higher NOM levels was attributed to Euaq complexation to NOMaq being more favored than Eu sorption to the solid phase. A component additivity model was developed to describe the Eu–NOM-sediment system by the additive effects of the three binary system models: Eu–NOM, Eu-sediment and NOM-sediment. The model generally captured the data trends in the ternary system. Conditional stability constants developed from the experimental data for the complexation of Eu to NOMsed were as much as four orders of magnitude greater than Eu complexation with NOMaq, presumably due to the NOMsed deriving additional negative (attractive) charge from the sediment surface. At high initial NOMaq levels, >99 mg/L C, the model captured the trend of reduced Eu sorption but tended to over-estimate Eu sorption. The additivity approach of combining binary models to form a ternary model was only successful when the unique complexation properties of the NOMsed were properly calculated.  相似文献   

5.
Time-resolved U(VI) laser fluorescence spectra (TRLFS) were recorded for a series of natural uranium-silicate minerals including boltwoodite, uranophane, soddyite, kasolite, sklodowskite, cuprosklodowskite, haiweeite, and weeksite, a synthetic boltwoodite, and four U(VI)-contaminated Hanford vadose zone sediments. Lowering the sample temperature from RT to ∼ 5.5 K significantly enhanced the fluorescence intensity and spectral resolution of both the minerals and sediments, offering improved possibilities for identifying uranyl species in environmental samples. At 5.5 K, all of the uranyl silicates showed unique, well-resolved fluorescence spectra. The symmetric O = U = O stretching frequency, as determined from the peak spacing of the vibronic bands in the emission spectra, were between 705 to 823 cm−1 for the uranyl silicates. These were lower than those reported for uranyl phosphate, carbonate, or oxy-hydroxides. The fluorescence emission spectra of all four sediment samples were similar to each other. Their spectra shifted minimally at different time delays or upon contact with basic Na/Ca-carbonate electrolyte solutions that dissolved up to 60% of the precipitated U(VI) pool. The well-resolved vibronic peaks in the fluorescence spectra of the sediments indicated that the major fluorescence species was a crystalline uranyl mineral phase, while the peak spacing of the vibronic bands pointed to the likely presence of uranyl silicate. Although an exact match was not found between the U(VI) fluorescence spectra of the sediments with that of any individual uranyl silicates, the major spectral characteristics indicated that the sediment U(VI) was a uranophane-type solid (uranophane, boltwoodite) or soddyite, as was concluded from microprobe, EXAFS, and solubility analyses.  相似文献   

6.
Surface complexation models (SCMs) are widely utilized as a tool to study the mobility of radionuclide to the environment. In this study, two SCMs, electrostatic (ES) and non-electrostatic (NES) models are employed in order to simulate the sorption behavior of U(VI) on quartz in the absence of Mg, Ca, and Sr and ES model in the presence of alkaline earth metals. The surface reaction constants (log K) for ES and NES models were fitted to experimental data by coupling PEST with PHREEQC. The SCM prediction of U(VI) sorption on quartz in the absence of alkaline earth metals is in good agreement with the experimental data in the pH range 6.5–9. The estimated log K values are sensitive to both ES and NES model calculations. In U(VI)-Mg-quartz, U(VI)-Ca-quartz, and U(VI)-Sr-quartz systems, only the ES model shows the general trend of the experimental data. The estimated log K values are sensitive with respect to the surface reactions. Hence, the ES model is more suitable for model calculations of the U(VI)-Mg-quartz, U(VI)-Ca-quartz, and U(VI)-Sr-quartz systems.  相似文献   

7.
Uranium(VI), which is often elevated in granitoidic groundwaters, is known to adsorb strongly to Fe (hydr)oxides under certain conditions. This process can be used in water treatment to remove U(VI). To develop a consistent geochemical model for U(VI) adsorption to ferrihydrite, batch experiments were performed and previous data sets reviewed to optimize a set of surface complexation constants using the 3-plane CD-MUSIC model. To consider the effect of dissolved organic matter (DOM) on U(VI) speciation, new parameters for the Stockholm Humic Model (SHM) were optimized using previously published data. The model, which was constrained from available X-ray absorption fine structure (EXAFS) spectroscopy evidence, fitted the data well when the surface sites were divided into low- and high-affinity binding sites. Application of the model concept to other published data sets revealed differences in the reactivity of different ferrihydrites towards U(VI). Use of the optimized SHM parameters for U(VI)-DOM complexation showed that this process is important for U(VI) speciation at low pH. However in neutral to alkaline waters with substantial carbonate present, Ca–U–CO3 complexes predominate. The calibrated geochemical model was used to simulate U(VI) adsorption to ferrihydrite for a hypothetical groundwater in the presence of several competitive ions. The results showed that U(VI) adsorption was strong between pH 5 and 8. Also near the calcite saturation limit, where U(VI) adsorption was weakest according to the model, the adsorption percentage was predicted to be >80%. Hence U(VI) adsorption to ferrihydrite-containing sorbents may be used as a method to bring down U(VI) concentrations to acceptable levels in groundwater.  相似文献   

8.
Radioactive core samples containing elevated concentrations of Cr from a high level nuclear waste plume in the Hanford vadose zone were studied to asses the future mobility of Cr. Cr(VI) is an important subsurface contaminant at the Hanford Site. The plume originated in 1969 by leakage of self-boiling supernate from a tank containing REDOX process waste. The supernate contained high concentrations of alkali (NaOH ≈ 5.25 mol/L), salt (NaNO3/NaNO2 >10 mol/L), aluminate [Al(OH)4− = 3.36 mol/L], Cr(VI) (0.413 mol/L), and 137Cs+ (6.51 × 10−5 mol/L). Water and acid extraction of the oxidized subsurface sediments indicated that a significant portion of the total Cr was associated with the solid phase. Mineralogic analyses, Cr valence speciation measurements by X-ray adsorption near edge structure (XANES) spectroscopy, and small column leaching studies were performed to identify the chemical retardation mechanism and leachability of Cr. While X-ray diffraction detected little mineralogic change to the sediments from waste reaction, scanning electron microscopy (SEM) showed that mineral particles within 5 m of the point of tank failure were coated with secondary, sodium aluminosilicate precipitates. The density of these precipitates decreased with distance from the source (e.g., beyond 10 m). The XANES and column studies demonstrated the reduction of 29-75% of the total Cr to insoluble Cr(III), and the apparent precipitation of up to 43% of the Cr(VI) as an unidentified, non-leachable phase. Both Cr(VI) reduction and Cr(VI) precipitation were greater in sediments closer to the leak source where significant mineral alteration was noted by SEM. These and other observations imply that basic mineral hydrolysis driven by large concentrations of OH− in the waste stream liberated Fe(II) from the otherwise oxidizing sediments that served as a reductant for CrO42−. The coarse-textured Hanford sediments contain silt-sized mineral phases (biotite, clinochlore, magnetite, and ilmenite) that are sources of Fe(II). Other dissolution products (e.g., Ba2+) or Al(OH)4− present in the waste stream may have induced Cr(VI) precipitation as pH moderated through mineral reaction. The results demonstrate that a minimum of 42% of the total Cr inventory in all of the samples was immobilized as Cr(III) and Cr(VI) precipitates that are unlikely to dissolve and migrate to groundwater under the low recharge conditions of the Hanford vadose zone.  相似文献   

9.
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 Kd 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.  相似文献   

10.
The effect of Mg-, Ca-, and Sr–Uranyl-Carbonato complexes with respect to sorption on quartz was studied by means of batch experiments with U(VI) concentration of 0.126 × 10−6 M in the presence and absence of Mg, Ca, and Sr (each 1 mM) at pH from 6.5 to 9. In the absence of alkaline earth elements, 90% of the U(VI) sorbed on the quartz surface at all pH. In the presence of Mg, Ca, and Sr, the sorption of U(VI) on quartz decreased to 50, 10, and 30%, respectively. Sorption kinetics of U(VI) on quartz is faster in the absence of alkaline earth elements and reached equilibrium after 12 h, whereas in the presence of Mg, Ca and Sr, the kinetics of U(VI) sorption on quartz is pH dependent and attained equilibrium after 24 h. Aqueous speciation calculations for alkaline earth uranyl carbonates were carried out by using PHREEQC with the Nuclear Energy Agency thermodynamic database (NEA_2007) by adding constants for MUO2(CO3)32− and M2UO2(CO3)30 (M = Ca, Mg, Sr). This study reveals that alkaline earth elements can have a significant effect on the aqueous speciation of U(VI) under neutral to alkaline pH conditions and subsequently sorption behavior and mobility of U(VI) in aqueous environments.  相似文献   

11.
In order to better understand the interaction between aqueous uranium and pyrite (FeS2) the uptake of uranium onto the surfaces of both weathered and freshly generated pyrite surfaces was examined using batch sorption experiments. Analysis was performed using X-ray photoelectron spectroscopy (XPS). The results clearly indicate that freshly polished pyrite surfaces are efficient scavengers of uranium from solution, while weathered surfaces exhibit only limited uptake. Results also indicate partial reduction of uranium at the pyrite surfaces, with a heterogeneous distribution of U(IV) and U(VI) species.  相似文献   

12.
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.  相似文献   

13.
《Geochimica et cosmochimica acta》1999,63(19-20):2891-2901
A long-standing problem in aquatic geochemistry has been the incorporation of natural organic matter (NOM) into speciation models. The general effect of NOM on metal ion sorption by particles has been understood for some time, and significant progress has been made in elucidating some of the details of the role of NOM through the use of surrogate organic acids such as citric acid. However, a gap exists between the general observations that have been made of NOM behavior and the inclusion of NOM in surface chemical models for metal ion sorption. In this paper, we report on the results of a study on the sorption of U(VI) by hematite in the absence and presence of Suwannee river humic acid (HA) and over a range of other system conditions (e.g., pH, I). Essential HA characteristics (e.g., its acid/base, metal binding, and surface chemical properties) were “captured” by representing the HA as an assembly of monoprotic acids with assumed pK values and without explicit correction for electrostatic effects. The ternary system (hematite/HA/U(VI)) was simulated through the combination of the binary submodels (i.e., CO32−/hematite, U(VI)/HA, U(VI)/hematite, and HA/hematite) with model constants fixed at the values determined from simulations of the respective experimental systems. However, the “summed-binary” approach undersimulated experimental results, and the ternary system model required the postulation of two ternary surface (Type A) complexes composed of the uranyl ion, hematite surface sites, and the model ligands comprising the HA. Consideration of the HA in this manner permitted the simulation of HA effects on U(VI) sorption by hematite over a range of solution conditions using a general speciation model.  相似文献   

14.
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).  相似文献   

15.
Many studies have proposed that silicic acid and phosphate (PV) can displace arsenic sorbed to iron oxides leading to elevated As concentrations in aquatic systems. While surface complexation models are adept at quantifying sorption to synthetic oxides in laboratory systems their application to complex natural systems remains challenging. In this study we provide a systematic approach to developing a robust use of models for understanding AsV distribution in natural systems in which hydrated iron oxides are the main adsorptive phase. The Waikato River provides a useful laboratory for this work because it contains high H4SiO4, AsV and PV loadings due to geothermal and agricultural inputs. A 15 min oxalate extraction and a 48 h ethylenediaminetetraacetic acid (EDTA) extraction of river sediment contained the same ratios of As:Fe, P:Fe and Si:Fe. Both of these extracts target the poorly ordered iron oxide phases (typically ferrihydrite) and by following the release of elements over time in the EDTA extraction it was possible to demonstrate that the extracted As, P, and Si were associated with the ferrihydrite. This demonstrates for the first time that a single oxalate extraction can quantify ferrihydrite sorbed H4SiO4, As and PV and provides a basis to quantify the role of these ligands in inhibiting AsV sorption to sediments. The measured concentrations of ferrihydrite sorbed AsV, PV and H4SiO4 for the Waikato River suspended sediment allow for the informed selection of appropriate model parameters for applying the Diffuse Layer Model to the system. In this way it was possible to quantify the effect of the individual components in the river water on AsV sorption. This study provides an explanation for the observation that the proportion of sorbed As in the Waikato River is generally significantly lower than that observed in rivers closer to the world average concentrations. More generally the study provides a method to quantify the role of individual water chemistry components on AsV distribution in natural systems.  相似文献   

16.
Lead sorption efficiencies of natural and synthetic Mn and Fe-oxides   总被引：1，自引：0，他引：1  
Lead sorption efficiencies (sorption per specific surface area) were measured for a number of natural and synthetic Mn and Fe-oxides using a flow-through reactor. The Mn-oxide phases examined included synthetic birnessite, natural and synthetic cryptomelane, and natural and synthetic pyrolusite; the Fe-oxides studied were synthetic akaganéite, synthetic ferrihydrite, natural and synthetic goethite, and natural and synthetic hematite. The sorption flow study experiments were conducted with 10 ppm Pb with an ionic strength of either 0.01 M NaNO3 or 0.01 M KNO3, both at pH 5.5. The experimental effluent solution was analyzed using aqueous spectroscopic methods and the reacted solids were analyzed using microscopy (field emission scanning electron microscopy, FE-SEM), structure analysis (powder X-ray diffraction, XRD), bulk chemical spectroscopy (energy dispersive spectroscopy, EDS), and surface sensitive spectroscopy (X-ray photoelectron spectroscopy, XPS). Overall and under these conditions, the synthetic Mn-oxides have higher sorption efficiencies than the natural Mn-oxides, which in turn are higher than the natural and synthetic Fe-oxides. Only natural pyrolusite had a sorption efficiency as low as the Fe-oxides. Most of the natural and synthetic Fe-oxides examined in this study removed about the same amount of Pb from solution once normalized to BET N2 surface area, although synthetic akaganéite and hematite were significantly less reactive than the rest.It is suggested that the observed efficiency of Mn-oxides for Pb sorption is directly related to internal reactive sites in the structures that contain them (birnessite and cryptomelane, in the case of this study). Comparisons of solution data to XPS data indicated that Pb went into the interlayer of the birnessite, which was supported by XRD; similarly some Pb may go into the tunnels of the cryptomelane structure. Layer structures such as birnessite have the highest Pb sorption efficiency, while the 2 × 2 tunnel structure of cryptomelane has lower efficiencies than birnessite, but higher efficiencies than other Mn- or Fe-oxide structures without internal reactive sites.  相似文献   

17.
Past mining, processing, and waste disposal activities have left a legacy of uranium-contaminated soil and groundwater. Phosphate addition to subsurface environments can potentially immobilize U(VI) in-situ through interactions with uranium at mineral-water interfaces. Phosphate can induce the precipitation of low solubility U(VI)-phosphates, and it may enhance or inhibit U(VI) adsorption to iron(III) (oxy)hydroxide surfaces. Such surfaces may also facilitate the heterogeneous nucleation of U(VI)-phosphate precipitates. The interactions among phosphate, U(VI), and goethite (α-FeOOH) were investigated in a year-long series of experiments at pH 4. Reaction time, total U(VI), total phosphate, and the presence and absence of goethite were systematically varied to determine their effects on the extent of U(VI) uptake and the dominant uranium immobilization mechanism. Dissolved U(VI) and phosphate concentrations were interpreted within a reaction-based modeling framework that included dissolution-precipitation reactions and a surface complexation model to account for adsorption. The best available thermodynamic data and past surface complexation models were integrated to form an internally consistent framework. Additional evidence for the uptake mechanisms was obtained using scanning electron microscopy and X-ray diffraction. The formation and crystal growth of a U(VI)-phosphate phase, most likely chernikovite, UO2HPO4·4H2O(s), occurred rapidly for initially supersaturated suspensions both with and without goethite. Nucleation appears to occur homogeneously for almost all conditions, even in the presence of goethite, but heterogeneous nucleation was likely at one condition. The U(VI)-phosphate solids exhibited metastability depending on the TOTU:TOTP ratio. At the highest phosphate concentration studied (130 μM), U(VI) uptake was enhanced due to the likely formation of a ternary surface complex for low (∼1 μM) to intermediate (∼10 μM) TOTU concentrations and to U(VI)-phosphate precipitation for high TOTU (∼100 μM) concentrations. For conditions favoring precipitation, the goethite surface acted as a sink for dissolved phosphate that resulted in higher dissolved U(VI) concentrations relative to goethite-free conditions. Based on the total uranium and available sorption sites, a critical phosphate concentration between 15 μM and 130 μM was required for preferential precipitation of uranium phosphate over U(VI) adsorption.  相似文献   

18.
We determined the association of uranium in yeast cells S. cerevisiae grown in medium containing high (1 g · L-1) or low (0.2 g · L-1) concentrations of phosphate after exposure for 96 h to a 4 × 10-4 mol · L-1 U(VI) solution at pH 3.2 or 4.7. The analysis was made using a field emission scanning electron microscope equipped with energy dispersive spectroscopy (FESEM-EDS), transmission electron microscopy (TEM), and visible diffuse reflectance spectrometry. Cells grown in the high-phosphate medium rapidly accumulated U(VI) from solution at pH 3.2 over the first 24 h, followed by a slow uptake until 96 h, whereas in cells grown in low-phosphate medium, U(VI) accumulation reached a steady state within 24 h. FESEM-EDS analyses revealed the formation of a U(VI)-bearing precipitate on the yeast cells grown in high-phosphate medium after only 48 h exposure; no precipitate was detected on cells grown in low-phosphate medium up to 96 h. These results suggest that sorption onto the cell surfaces was the dominant process initially. Analysis of the U(VI)-bearing precipitates by all three methods demonstrated the presence of H-autunite, HUO2PO4 · 4H2O. Thermodynamic calculations suggest that the chemical compositions of the solutions containing yeast grown in high-phosphate medium were undersaturated with respect to H-autunite, but were supersaturated with ten times more U(VI) and P than were actually observed. Apparently, the sorbed U(VI) on the cell surfaces reacts with P released from the yeast to form H-autunite by local saturation. The U(VI) uptake by yeast cells grown in high phosphate medium at pH 4.7, along with the thermodynamic calculation, indicated that more H-autunite is precipitated in neutral pH solution than in acid solution. Thus, U(VI)-phosphate mineralization on the cells of microorganisms should be taken into account for predicting U(VI) mobility in the environment.  相似文献   

19.
Reductive dissolution of arsenic-bearing ferrihydrite   总被引：2，自引：0，他引：2  
Ferrihydrites were prepared by coprecipitation (COP) or adsorption (ADS) of arsenate, and the products were characterized using solid-state methods. In addition, the kinetics of reductive dissolution by hydroquinone of these well-characterized materials were quantified. Characterization and magnetism results indicate that the 10 wt% As COP ferrihydrite is less crystalline and possibly has smaller crystallite size than the other ferrihydrites, which all have similar crystallinity and particle size. The results from reductive dissolution experiments show similar reaction rates, reaction mechanism, and activation energy for ferrihydrite precipitated with or without added arsenate. However, a marked decrease in reactivity was observed for 10 wt% As ADS ferrihydrite. The decrease is not attributed to differences in activation energy but rather the preferential blocking of active sites on the ferrihydrite surface. Results demonstrate that arsenic may be released by the reductive dissolution of arsenic-bearing ferrihydrite regardless of whether the arsenic is coprecipitated with or adsorbed onto the ferrihydrite. However, under these reaction conditions, release from materials with adsorbed arsenate greatly exceeds that from materials with coprecipitated arsenate. In fact, a considerable amount of arsenic was released from the 10 wt% ADS ferrihydrite before reductive dissolution was initiated. Therefore, the characterization of arsenate-bearing iron oxide materials to determine the method of arsenate incorporation into structures—perhaps by quantification of Fe-Fe coordination with EXAFS spectroscopy—may lead to improved predictions of the large-scale release of arsenic within aquifer systems under reducing conditions.  相似文献   

20.
The effect of dissolved organic matter (DOM) on Am(III), Pu(IV), Np(V), and U(VI) sorption was investigated with natural water (pH ∼8) and zeolitized tuff samples collected from the Rainier Mesa tunnel system, Nevada Test Site, where the USA detonated underground nuclear tests prior to 1992. Perched vadose zone water at Rainier Mesa has high levels of DOM as a result of microbial degradation of mining debris (diesel, wood, etc.). The Am and Pu sorption Kds were up to two orders of magnitude lower in water with high DOM (15-19 mg C/L) compared to the same water with DOM removed (<0.4 mg C/L) or in naturally low DOM (0.2 mg C/L) groundwater. In contrast, Kds of Np and U were less affected by DOM at these solution conditions. Uranium sorption decreased as a result of high dissolved inorganic C (DIC) resulting from microbial degradation of DOM. Thermodynamic model predictions, based on actinide-humic acid stability constants available in the literature, are in general agreement with measured Kd data, correctly predicting the effects of DIC and DOM on actinide retardation. This agreement is encouraging to future modeling efforts and suggests that effects of DOM and DIC can be incorporated into reactive transport modeling predictions. The Am and Pu transport rates in Rainier Mesa tunnel waters will be substantially faster as a result of the elevated DOM levels. Low diffusion rates of actinide-DOM macromolecular complexes may focus Pu and Am transport into fractures and minimize retardation via matrix diffusion. The resulting transport behavior will affect actinide distribution patterns and associated risk estimates.  相似文献   

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