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1.
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   

2.
Proton binding constants for the edge and basal surface sites of kaolinite were determined by batch titration experiments at 25 °C in the presence of 0.1 M, 0.01 M and 0.001 M solutions of NaNO3 and in the pH range 3-9. By optimizing the results of the titration experiments, the ratio of the edge sites to the basal surface sites was found to be 6:1. The adsorption of Cd(II), Cu(II), Ni(II), Zn(II) and Pb(II) onto kaolinite suspensions was investigated using batch adsorption experiments and results suggested that in the lower pH range the metallic cations were bound through non-specific ion exchange reactions on the permanently charged basal surface sites (X−). Adsorption on these sites was greatly affected by ionic strength. With increasing pH, the variable charged edge sites (SOH) became the major adsorption sites and inner-sphere specifically adsorbed monodentate complexes were believed to be formed. The effect of ionic strength on the extent of adsorption of the metals on the variable charged edge sites was much less than those on the permanently charged sites. Two binding constants, log K(X2Me) and log K(SOMe), were calculated by optimizing these constants in the computer program FITEQL. A model combining non-specific ion exchange reactions and inner-sphere specific surface complexations was developed to predict the adsorption of heavy metals onto kaolinite in the studied pH range. Linear free energy relationships were found between the edge site binding constants and the first hydrolysis constants of the metals.  相似文献   

3.
《Geochimica et cosmochimica acta》1999,63(19-20):2939-2955
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4.
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5.
In solution thermodynamics, and more recently in surface chemistry, it is well established that relationships can be found between the free energies of formation of aqueous or surface metal complexes and thermodynamic properties of the metal ions or ligands. Such systematic dependencies are commonly termed linear free energy relationships (LFER). A 2 site protolysis non-electrostatic surface complexation and cation exchange (2SPNE SC/CE) model has been used to model “in house” and literature sorption edge data for eleven elements: Mn(II), Co(II), Ni(II), Zn(II), Cd(II), Eu(III), Am(III), Sn(IV), Th(IV), Np(V) and U(VI) to provide surface complexation constants for the strong sites on montmorillonite. Modelling a further 4 sets of sorption isotherms for Ni(II), Zn(II), Eu(III) and U(VI) provided complexation constants for the weak sites. The protolysis constants and site capacities derived for the 2SPNE SC/CE model in previous work were fixed in all of the calculations. Cation exchange was modelled simultaneously to provide selectivity coefficients. Good correlations between the logarithms of strong SKx−1 and weak W1Kx−1 site binding constants on montmorillonite and the logarithm of the aqueous hydrolysis constants OHKx were found which could be described by the following equations: Strong (≡SSOH) sites:
SlogKX−1=8.1±0.3+(0.90±0.02)logOHKX  相似文献   

6.
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   

7.
Amorphous tin(VI) hydrogen phosphate (ATHP) was synthesized using the liquid phase precipitation method and served as an adsorbent to remove Pb(II), Cu(II), and Zn(II) from aqueous solutions. The ATHP was characterized by powder X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and nitrogen adsorption–desorption techniques. Adsorption properties were evaluated as a function of pH, reaction time, concentration of reactants, and salinity. Their equilibrium adsorption data were modeled using Freundlich, Langmuir, and Dubinin–Kaganer–Radushkevich isotherms, respectively. The results revealed that adsorption equilibrium reached within 180 min. ATHP indicated good adsorption even below the pHZPC, and best adsorption at pH 5 for Pb(II) and Cu(II) and at pH 5.5 for Zn(II) was observed. Equilibrium data fitted better to the Langmuir model for Pb(II) and Cu(II) and fitted better to the Freundlich model for Zn(II). The saturated adsorption capacities deduced from the Langmuir model were 2.425, 1.801, and 0.600 mmol/g for Cu(II), Pb(II), and Zn(II), respectively, indicating an adsorption affinity order of Cu > Pb > Zn. There is a negative correlation between the concentration of NaCl and adsorption capacity of ATHP, yet ATHP still exhibited excellent adsorption having an adsorption capacity of 19.35, 15.16, 6.425 mg/g when the concentration of NaCl was 0.6 mol/L. The free energy (E) was 12.33, 10.70, and 14.74 kJ/mol for Pb(II), Cu(II), and Zn(II), respectively. An adsorption mechanism based on ion exchange between heavy metal ions and H+ in the ATHP is proposed. Furthermore, the used ATHP was regenerated by HCl solution and the adsorbent was used repeatedly.  相似文献   

8.
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   

9.
《Applied Geochemistry》2006,21(9):1539-1550
Microbial processes have the potential to affect the mobility of radionuclides, including U in radioactive wastes. A range of geochemical, molecular biological and mineralogical techniques were applied to investigate stable element biogeochemistry and U solubility in the simulated “near-field” (or local environment) of a low-level radioactive waste (LLW) repository. The experiments used a microbial inoculum from the trench disposal area of the UK LLW repository at Drigg, Cumbria, England, in combination with a synthetic trench leachate representing the local environment at the Drigg site. In batch culture experiments in the absence of U, a classic redox progression of terminal electron accepting processes (TEAPs) occurred in the order NO3-, Fe(III) and SO42- reduction. When 126 μM U was added to the system as U(VI)aq, up to 80% was reduced to U(IV) by the indigenous microbial consortium. The U(IV) was retained in solution in these experiments, most likely by complexation with citrate present in the experimental medium. No U(VI)aq was reduced in sterile cultures, confirming that U(VI)aq reduction was microbially mediated. Interestingly, when U(VI)aq was present, the progression of TEAPs was altered. The rate of Fe(III) reduction slowed compared to experiments without U(VI)aq, and SO4 reduction occurred at the same time as U(VI) reduction. Finally, an experiment where SO42--reducing microorgansisms were inhibited by Na molybdate showed no ingrowth of sulfide minerals, but U(VI) reduction continued in this experiment. This suggested that sulfide minerals did not play a significant role in abiotically reducing U(VI) in these systems, and that metal-reducing microorganisms were dominant in mediating U(VI) reduction. Bacteria closely related to microorganisms found in engineered and U-contaminated environments dominated in the experiments. Denaturing gradient gel electrophoresis (DGGE) on 16SrRNA products amplified from broad specificity primers showed that after incubation, differences in diversity and abundance of the microbial culture were observed between U and non-U experiments. These results indicate that the biogeochemistry of the LLW repository near-field stimulates reduction of U(VI)(aq) to U(IV) under anaerobic conditions and that the fate of reduced U(IV) will depend on the complexants present in LLW systems.  相似文献   

10.
《Applied Geochemistry》2002,17(4):399-408
The sorption of U(VI) onto the surface of olivine has been experimentally investigated at 25 °C under an air atmosphere as a function of pH, solid surface to volume ratio and total U concentration. Sorption has been observed to decrease as the extent of carbonate complexation of U(VI) in solution increases, which is attributed to the competition between aqueous and solid ligands for the coordination of U. The experimental results have been interpreted by means of two different approaches: (1)a semi-empirical model, exemplified by the application of a Langmuir isotherm and (2) a non-electrostatic thermodynamic surface complexation model which includes the formation of the surface species: >SO–UO2+ and >SO–UO2(OH). The following stability constants for these species have been determined from the thermodynamic analysis: K(>SO–UO2+)=289±71 and K(>SO–UO2(OH))=(3.4±0.4)×10−6. The comparison of the sorption of U onto olivine with granites of different origin indicate that the use of this mineral as additive to the backfill of deep high level nuclear waste repositories could retard the migration of U from the repository to the geosphere.  相似文献   

11.
Remediation of U-contaminated sites relies upon thermodynamic speciation calculations to predict U(VI) movement in the subsurface. However, reliability and applicability of geochemical speciation and reactive transport models may be limited by determinate (model) errors and random (uncertainty) errors in the equilibrium speciation calculations. This study examines propagated uncertainty in two types of subsurface calculations: I. Dissolved U(VI) speciation based on measured analytical constraints and solution phase equilibria and II. Overall U(VI) speciation which combined the dissolved phase equilibria with previously published adsorption reactions. Three levels of uncertainty, instrumental uncertainty, temporal variation and spatial variation across a site, were investigated using first-derivative sensitivity calculations and Monte Carlo simulations. Dissolved speciation calculations were robust, with minimal amplification of uncertainty and normal output distributions. The most critical analytical constraints in the dissolved system are pH, DIC, total U and total Ca, with some effect from dissolved . When considering adsorption equilibria, calculations were robust with respect to adsorbed U(VI) concentration prediction, but bimodal distributions of dissolved U(VI) concentrations were observed in simulations with background levels of total U(VI) and higher (spatial and temporal variability) estimates of input uncertainty. Consequently, sorption model predictions of dissolved U(VI) may not be robust with respect these higher levels of uncertainty.  相似文献   

12.
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.  相似文献   

13.
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.  相似文献   

14.
The adsorption of uranyl (UO22+) on ferrihydrite has been evaluated with the charge distribution (CD) model for systems covering a very large range of conditions, i.e. pH, ionic strength, CO2 pressure, U(VI) concentration, and loading. Modeling suggests that uranyl forms bidentate inner sphere complexes at sites that do not react chemically with carbonate ions. Uranyl is bound by singly-coordinated surface groups present at particular edges of Fe-octahedra of ferrihydrite while another set of singly-coordinated surface groups may form double-corner bidentate complexes with carbonate ions. The uranyl surface speciation strongly changes in the presence of carbonate due to the specific adsorption of carbonate ions as well as the formation of ternary uranyl-carbonate surface complexes. Data analysis with the CD model suggests that a uranyl tris-carbonato surface complex, i.e. (UO2)(CO3)34−, is formed. This species is most abundant in systems with a high pH and carbonate concentration. This finding differs significantly from previous interpretations made in the literature. At high pH and low carbonate concentrations, as can be prepared in CO2-closed systems, the model suggests the additional presence of a ternary uranyl-monocarbonato complex. The binding mode (type A or type B complex) is uncertain. At high uranyl concentrations, uranyl polymerizes at the surface of ferrihydrite giving, for instance, tris-uranyl surface complexes with and without carbonate. The similarities and differences between U(VI) adsorption by goethite and ferrihydrite are discussed from a surface structural point of view.  相似文献   

15.
Experiments designed to simulate the dissolution of alkali feldspar during magma mixing produced plagioclase mantles that are texturally and compositionally similar to those in some hybrid volcanic rocks. In hydrous dacite melt (69% SiO2) at 0.8 GPa, 850°C, orthoclase (Or93) and sanidine (Or30) partially dissolved and were mantled by sodic plagioclase (An25–30). Although plagioclase nucleated epitaxially as a thin shell on the alkali feldspar surface near the time of initial resorption, plagioclase subsequently grew inward —mostly in the form of parallel blades — toaard the receding dissolution surface. Orthoclase dissolved at a rate approximately proportional to the square root of run duration, indicating diffusional control. Plagioclase grew inward within a static boundary zone of melt that formed between the original crystal-dacite interface and the dissolution surface. During orthoclase dissolution, this boundary zone rapidly and simultancously gained Na (by diffusion from dacite) and lost K (by diffusion into dacite); Ca diffused more slowly into this zone, from which non-feldspar species were mostly excluded. Plagioclase was stable where sufficient Ca had diffused in that the boundary zone melt intersected the plagioclase-saturation liquidus. Plagioclase subsequently grew toward the receding dissolution surface as the Ca compositional gradient (and hence the site of plagioclase saturation) stepped inward. Crystallization of plagioclase in the form of parallel blades allowed continued diffusive exchange of melt components between the dissolution surface and the host melt. Bladed growth also served to maintain (at blade tips) proximity of plagioclase to the dissolution surface, thereby apparently preserving (locally) a thin zone of low-variance melt. In natural systems, mantling of alkali feldspar by plagioclase will occur in a similar manner when (a) P, T, or X are changed to induce alkali feldspar dissolution, (b) sufficient Ca is available in the host melt to drive (by diffusion) boundary zone melt compositions to plagioclase saturation, and (c) temperatures are low enough to stabilize sodic plagioclase and to maintain a coherent boundary zone. These reqjirements are satisfied in volcanic systems when alkali feldspar is juxtaposed during mixing with hybrid melts of dacitic composition. Mantled feldspars in some intrusive systems (i.e., rapakivi granites) may form by a similar dissolution- and diffusion-controlled mechanism. Textural evidence of a similar origin may be obscurred in intrusive rocks, however, by products of late-stage magmatic and subsolidus processes.  相似文献   

16.
Extraordinarily high Pb content in K-feldspar and plagioclase has been found contiguous to monazite in two occurrences in the ultrahigh-temperature Napier Complex of Antarctica. Monazite shows a variety of textures and compositions. In a garnet-sillimanite-orthopyroxene paragneiss at Mount Pardoe (Amundsen Bay), grains range 80–150 μm across and are anhedral; two grains are Th- and Si-dominant. In pods that crystallized from anatectic melts at 2500 Ma at Zircon Point, Casey Bay, monazite grains range 0.05 mm–1 cm in length and are highly variable in texture. The coarsest grains (>0.7 cm) are skeletal and euhedral, whereas the smallest grains are anhedral and associated with fine- to medium-grained quartz, K-feldspar, plagioclase, garnet, sillimanite and rutile in aggregates that form interstitial veinlets interpreted to be a second generation of anatexis during an event at 1100 Ma. The huttonite component (ThSiO4) reaches 30 mole% in the cores of the coarsest skeletal grains, whereas other grains, particularly smaller ones, show complex and irregular zoning in Th and U. The latter zoning is attributed to dissolution-reprecipitation, which also resulted in complete Pb loss during the 1100 Ma event. In the paragneiss at Mount Pardoe, K-feldspar and myrmekitic plagioclase (An16) are found in a 70–80 μm band between monazite and orthopyroxene and contain up to 12.7 wt.% and 2.7 wt.% PbO, respectively, corresponding to 18.5% and 3.4% PbAl2Si2O8 component, respectively. Cathodoluminescence of both feldspars increases with distance from a nearby monazite grain and is not correlated with Pb content. Incorporation of Pb in K-feldspar and plagioclase could be a result of diffusion, even though the monazite adjacent to feldspar apparently lost little Pb, i.e., Pb could have been transported by fluid from the Th-rich grains, which did lose Pb. In contrast to the paragneiss, cathodoluminescence correlates with Pb content of K-feldspar in aureoles surrounding skeletal monazite grains 0.7–1 cm across in anatectic pods at Zircon Point. Pb content of K-feldspar decreases monotonically to near detection limits within several millimetres of monazite grains; the greatest PbO concentration is attained in K-feldspar inliers and embayments in monazite, 8.8 wt.%, corresponding to 11.7% PbAl2Si2O8 component. Fine-grained quartz in the K-feldspar suggests that the mechanism for Pb incorporation involved breakdown of feldspar: Pb2+ + 2(K,Na)AlSi3O8 → PbAl2Si2O8 + 4SiO2 + 2(K,Na)+ . The smooth decrease of Pb in the aureoles is not characteristic of dissolution-reprecipitation, which is characterized by abrupt changes of composition, and it seems more likely that Pb was incorporated in K-feldspar by diffusion at 1100 Ma. We suggest a model whereby fluid introduced during the 1100 Ma event flowed along grain boundaries and penetrated mineral grains. Temperatures were sufficiently high, i.e., 700°C, assuming burial in the mid-crust, for the fluid to induce localized melting of quartzofeldspathic matrix of the anatectic pods. Loss of radiogenic Pb was complete. Some penetration of K-feldspar by aqueous fluid is suggested by the presence of scattered galena specks and by rays of turbidity emanating from monazite. Aqueous fluid or water-rich granitic melt may have mediated the diffusion of Pb in feldspar, but it did not cause dissolution-reprecipitation. Although Pb was mobilized by aqueous fluid or water-rich granitic melt, it was not entirely flushed from the immediate vicinity of the monazite, but nearly half was incorporated in adjacent feldspar. Fluid activity that could cause Pb loss in monazite does not always leave an obvious trace, i.e., hydrous minerals, such as sericite, are very sparse, and biotite is absent in the anatectic pods at Zircon Point. Nonetheless, electron microprobe dating of monazite from the pods could not detect the 2500 Ma age of original crystallization determined by isotopic dating.  相似文献   

17.
Sorption interactions with montmorillonite and other clay minerals in soils, sediments, and rocks are potentially important mechanisms for attenuating the mobility of U(6+) and other radionuclides through the subsurface environment. Batch experiments were conducted (in equilibrium with atmospheric % MathType!MTEF!2!1!+-% feaafeart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXafv3ySLgzGmvETj2BSbqefm0B1jxALjhiov2D% aebbfv3ySLgzGueE0jxyaibaiiYdd9qrFfea0dXdf9vqai-hEir8Ve% ea0de9qq-hbrpepeea0db9q8as0-LqLs-Jirpepeea0-as0Fb9pgea% 0lrP0xe9Fve9Fve9qapdbaqaaeGacaGaaiaabeqaamaabaabcaGcba% acbiGaiWiG-bfadaWgaaWcbaacbaGaa43qaiaa+9eadaWgaaqaaiaa% +jdaaWqabaaaleqaaaaa!400D!\[P_{CO_2 } \])to determine the effects of varying pH (2 to 9), solid-mass to solution-volume ratio (M/V = 0.028 to 3.2 g/L), and solution concentration (2 × 10–7 and 2 × 10–6 M 233U) on U(6+) sorption on SAz-1 montmorillonite. The study focused on U(6+) surface complexation on hydroxylated edge sites as the sorption mechanism of interest because it is expected to be the predominant sorption mechanism at pHs typical of natural waters (pH 6 to 9). Thus, the experiments were conducted with a 0.1 M NaNO3 matrix to suppress ion-exchange between U(6+) in solution and interlayer cations. The results show that U(6+) sorption on montmorillonite is a strong function of pH, reaching a maximum at near-neutral pH (6 to 6.5) and decreasing sharply towards more acidic or more alkaline conditions. A comparison of the pH-dependence of U(6+) sorption with that of U(6+) aqueous speciation indicates a close correspondence between U(6+) sorption and the predominance field of U(6+)-hydroxy complexes. At high pH, sorption is inhibited due to formation of aqueous U(6+)-carbonate complexes. At low pH, the low sorption values indicate that the 0.1 M NaNO3 matrix was effective in suppressing ion-exchange between the uranyl (UO2 2+) species and interlayer cations in montmorillonite. At pH and carbonate concentrations typical of natural waters, sorption of U(6+) on montmorillonite can vary by four orders of magnitude and can become negligible at high pH.The experimental results were used to develop a thermodynamic model based on a surface complexation approach to permit predictions of U(6+) sorption at differing physicochemical conditions. A Diffuse-Layer model (DLM) assuming aluminol (>AlOH) and silanol (>SiOH) edge sites and two U(6+) surface complexation reactions per site effectively simulates the complex sorption behavior observed in the U(6+)-H2O-CO2-montmorillonite system at an ionic strength of 0.1 M and pH > 3.5. A comparison of model predictions with data from this study and from published literature shows good agreement and suggests that surface complexation models based on parameters derived from a limited set of data could be useful in extrapolating radionuclide sorption over a range of geochemical conditions. Such an approach could be used to support transport modeling by providing a better alternative to the use of constant K d s in transport calculations.  相似文献   

18.
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).  相似文献   

19.
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   

20.
Uranium(VI) sorption onto kaolinite was investigated as a function of pH (3–12), sorbate/sorbent ratio (1 × 10?6–1 × 10?4 M U(VI) with 2 g/L kaolinite), ionic strength (0.001–0.1 M NaNO3), and pCO2 (0–5%) in the presence or absence of 1 × 10?2–1 × 10?4 M citric acid, 1 × 10?2–1 × 10?4 M EDTA, and 10 or 20 mg/L fulvic acid. Control experiments without-solids, containing 1 × 10?6–1 × 10?4 M U(VI) in 0.01 M NaNO3 were used to evaluate sorption to the container wall and precipitation of U phases as a function of pH. Control experiments demonstrate significant loss (up to 100%) of U from solution. Although some loss, particularly in 1 × 10?5 and 1 × 10?4 M U experiments, is expected due to precipitation of schoepite, adsorption on the container walls is significant, particularly in 1 × 10?6 M U experiments. In the absence of ligands, U(VI) sorption on kaolinite increases from pH ～3 to 7 and decreases from pH ～7.5 to 12. Increasing ionic strength from 0.001 to 0.1 M produces only a slight decrease in U(VI) sorption at pH < 7, whereas 10% pCO2 greatly diminishes U(VI) sorption between pH ～5.5 and 11. Addition of fulvic acid produces a small increase in U(VI) sorption at pH < 5; in contrast, between pH 5 and 10 fulvic acid, citric acid, and EDTA all decrease U(VI) sorption. This suggests that fulvic acid enhances U(VI) sorption slightly via formation of ternary ligand bridges at low pH, whereas EDTA and citric acid do not form ternary surface complexes with the U(VI), and that all three ligands, as well as carbonate, form aqueous uranyl complexes that keep U(VI) in solution at higher pH.  相似文献   

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