Sorption of U(VI) onto granite surfaces: A kinetic approach

Surface sorption experiments of U(VI) onto the surfaces of a Korean granite rock are carried out in order to investigate the kinetics and reversibility of U(VI) sorption as a function of pH and surface types such as fresh intact surfaces and natural fracture surfaces. It was shown that the effect of pH is significant in the sorption of U(VI) onto both types of the granite surfaces. However the sorption rates do not greatly depend upon the pH regardless of the surface types. A two-step first order kinetic behavior dominates onto both the intact surfaces and natural fracture surfaces of granite and that the linearization approach of the kinetic model agrees well with experimental sorption data. The desorption results showed that the sorption process of U(VI) was a little irreversible for the two types of granite surfaces regardless of pH and surface types. This kinetic approach could give a better understanding of U(VI) sorption onto granite surfaces depending on pH and surface types. This revised version was published online in July 2006 with corrections to the Cover Date.     

Retention of uranium(VI) by laumontite, a fracture-filling material of granite

Retention of U(VI) by laumontite, a fracture-filling material of granite was investigated by conducting dynamic and batch sorption experiments in a glove-box using a granite core with a natural fracture. The hydrodynamic properties of the granite core were obtained from the elution curve of a non-sorbing tracer, Br⁻. The elution curve of U(VI) showed a similar behavior to Br⁻. This reveals that the retention of U(VI) by the fracture-filling material was not significant when migrating through the fracture at a given condition. From the dynamic sorption experiment, the retardation factor R _a and the distribution coefficient K _a of U(VI) were obtained as about 2.9 and 0.16 cm, respectively. The distribution coefficient (K _d ) of U(VI) onto laumontite obtained by conducting a batch sorption experiment resulted in a small value of 2.3±0.5 mL/g. This low K _d value agreed with the result of the dynamic sorption experiment. For the distribution of uranium on the granite surface investigated by an X-ray image mapping, the fracture region filled with laumontite showed a relatively lower content of uranium compared to the surrounding granite surface. Thus, the low retention of U(VI) by the fracture-filling material can be explained by following two mechanisms. One is that U(VI) exists as anionic uranyl hydroxides or uranyl carbonates at a given groundwater condition and the other is the remarkably low sorption capacity of the laumontite for U(VI).     

Comparative study on retardation behavior of Cs in crushed and intact rocks: two potential repository host rocks in the Taiwan area

This study investigates sorption and diffusion of Cs in two potential host rocks (granite from Kinmen Island and basalt from Penghu Island) by using batch and through-diffusion methods in order to establish a reliable safety assessment methodology. These methods were applied to crushed and intact rock samples to investigate the actual geological environment. According to solid-phase analysis, including X-ray diffraction, elemental analysis, auto radiography, and polar microscopy, the sorption component primarily contained iron?Cmagnesium (Fe?CMg) minerals in basalt and granite. Moreover, the distribution coefficient (K _d) of Cs in various concentrations (~10^?2?C10^?7?M) obtained from batch tests indicated a higher sorption capacity in basalt than that in granite because of the 10% Fe?CMg mineral content. The diffusion of Cs in both crushed granite and basalt reached steady state after 110?days, and the apparent diffusion coefficients (D _a) were 2.86?×?10^?11 and 1.82?×?10^?12?m²/s, respectively. However, the value of D _a for Cs in intact rocks was estimated to be 1.45?×?10^?12?m²/s in granite and 0.56?×?10^?12?m²/s in basalt, lower than the values obtained using crushed rocks. In addition to the microporous structure (major sorption minerals), it showed that the major retardation of Cs depended on the porosity (??) of compacted media, according to through-diffusion tests. In fact, the solid/liquid (S/L) ratio decreased as is the case when switching from batch to column experiments and the sorption effect on minerals became even more negligible in retardation of radionuclide migration.     

Simultaneous removal of uranium and humic acid by cyclodextrin modified graphene oxide nanosheets

Cyclodextrin-modified graphene oxide nanosheets (denoted as CD/GO) were synthesized by an in-situ polymerization method and characterized by as well as Fourier transform-infrared spectroscopy, X-ray photoelectron spectroscopy, Raman spectroscopy and potentiometric acid-base titration. The characterization results indicated that CD was successfully grafted onto GO surfaces by forming a chemical bond. Mutual effects on the simultaneous removal of hexavalent uranium and humic acid by CD/GO from aqueous solution were investigated. The results indicated that U(VI) and humic acid (HA) sorption on CD/GO were greatly affected by pH and ionic strength. The presence of HA enhanced U(VI) sorption at low pH and reduced U(VI) sorption at high pH, whereas the presence of U(VI) enhanced HA sorption. The surface adsorbed HA acted as a “bridge” between U(VI) and CD/GO, and formed strong inner-sphere surface complexes with U(VI). Sorption isotherms of U(VI) or HA on CD/GO could be well fitted by the Langmuir model. This work highlights that CD/GO can be used as a promising material in the enrichment of U(VI) and HA from wastewater in U(VI) and humic substances obtained by environmental pollution cleanup.     

Interaction of U(VI) with Na-attapulgite in the presence and absence of humic acid as a function of pH, ionic strength and temperature

The interaction of U(VI) with Na-attapulgite was studied by using batch technique at different experimental conditions. The effect of contact time, solid content, pH, ionic strength and temperature on the sorption of U(VI) onto Na-attapulgite in the presence and absence of humic acid was also investigated. The results showed that the sorption of U(VI) on Na-attapulgite achieved sorption equilibrium quickly. Sorption of U(VI) on Na-attapulgite increased quickly with increasing pH at pH < 6.5, and then decreased with pH increasing at pH > 6.5. The sorption curves were shifted to left in low NaClO₄ solutions as compared those in high NaClO₄ solutions. The sorption was strongly dependent on pH and ionic strength. The sorption was dominated by ion exchange or outer-sphere surface complexation at low pH values, and by inner-sphere surface complexation or surface precipitation at high pH values. The thermodynamic parameters (i.e., ΔH ⁰, ΔS ⁰, and ΔG ⁰) for the sorption of U(VI) were calculated from the temperature dependent sorption isotherms, and the results suggested that the sorption reaction was an endothermic and spontaneous process. The Na-attapulgite is a suitable material in the removal and preconcentration of U(VI) from large volumes of aqueous solutions in nuclear waste management.     

Sorption of U(VI) onto a decarbonated calcareous soil

Sorption of U(VI) from aqueous solution to decarbonated calcareous soil (DCS) was studied under ambient conditions using batch technique. Soil samples were characterized by XRD, FT-IR and SEM in detail and the effects of pH, solid-to-liquid ratio (m/V), temperature, contact time, fulvic acid (FA), CO₂ and carbonates on U(VI) sorption to calcareous soil were also studied in detail using batch technique. The results from experimental techniques showed that sorption of U(VI) on DCS was significantly influenced by pH values of the aqueous phase, indicating a formation of inner-sphere complexes at solid–liquid interface, and increased with increasing temperature, suggesting the sorption process was endothermic and spontaneous. Compared to Freundlich model, sorption of U(VI) to DCS was simulated better with Langmuir model. The sorption equilibrium could be quickly achieved within 5 h, and sorption results fitted pseudo-second-order model well. The presence of FA in sorption system enhanced U(VI) sorption at low pH and reduced U(VI) sorption at high pH values. In absence of FA, the sorption of U(VI) onto DCS was an irreversible process, while the presence of FA reinforced the U(VI) desorption process reversible. The presence of CO₂ decreased U(VI) sorption largely at pH >8, which might due to a weakly adsorbable formation of Ca₂UO₂(CO₃)₃ complex in aqueous phase.     

A triple continuum one-dimensional transport model for colloid facilitated contaminant migration in sets of parallel fractures with fracture skin

A triple continuum one-dimensional transport model is developed to analyse colloid facilitated contaminant transport in fractured geological formations. The model accounts for contaminant transport in the fracture, reversible deposition onto fracture surfaces and onto the colloids, diffusion into the rock formation and irreversible deposition of colloids onto the fracture surfaces. Sorption of the contaminant onto the fracture surfaces and onto suspended and deposited colloids are assumed to follow the linear equilibrium assumption (LEA); whereas the irreversible deposition of colloids onto the fracture skin surface is assumed to be governed by the linear kinetic sorption isotherms. The resulting coupled contaminant transport equations are solved using a numerical model employing fully implicit finite difference method based formulation. Results clearly demonstrate that the presence of the fracture skin significantly influences colloid facilitated contaminant migration in fractured formations. Fracture skin porosity and fracture skin diffusion coefficient are demonstrated to be the critical fracture skin properties that affect colloid facilitated contaminant migration in fractures. The impact of different colloid parameters on contaminant transport is investigated. The distribution coefficient for contaminant sorption onto the suspended colloids is found to be the most significant colloid related parameter influencing contaminant migration in fractured formation with fracture skin.     

Investigation of U(VI) desorption behavior from natural sediment,Oak Ridge

Investigation of U(VI) desorption from the natural sediment of Oak Ridge Field Research Center saprolite is of great importance to predict the fate and transport of U(VI) in the subsurface environment. After treatment by the dithonite- citrate-bicarbonate method, only 20% of U(VI) was extracted by 0.1 mol/L HNO₃ solution, indicating that the predominate adsorbed carrier of U(VI) in natural sediment was iron (hydr)oxides. Further evidence collected through a high resolution TEM investigation such as goethite observed in clay minerals. The desorption of U(VI) from PRFRC saprolite was satisfactorily fitted by surface complexation modeling at a low NaHCO₃ concentration starting from 0.001 to 0.1 mol/L, whereas appreciable over-estimation was observed at high concentrations of NaHCO₃. The uncertainty analysis method used in this study was an expanded uncertainty analysis method, and estimates with a 95% confidence interval (c) were obtained for these test data points. These observations revealed that the goethite with clay minerals played the vital role in U(VI) sorption and desorption behaviors in subsurface sediments.     

Interaction mechanisms of U(VI) and graphene oxide from the perspective of particle size distribution

Graphene oxide (GO) is an ideal adsorbent due to excellent physicochemical properties. Humic acid (HA) is ubiquitous in aquatic and soil environment, which can affect the migration of metal ions. In this study, we investigated the sorption mechanisms of U(VI) onto GO surfaces in the presence of HA. pH dependent and ionic strength independent sorption process were observed and the concentration of HA is positively proportional to U(VI) sorption capacities. Results also suggest that a pre-mixing HA + U(VI) gave better results than a pre-mixing of GO + HA, which can be explained by the size distribution of different GO systems.

     

Selective uranium adsorption using modified acrylamide resins

Polymeric matrices composed of N,N′-Methylenebis(acrylamide)/glycidyl methacrylate was prepared and modified producing two resins (GMA/MBA/OH and GMA/MBA/SO₃H). The adsorption of U(VI) ions onto the modified acrylamide resins was studied from synthetic and granite samples. For better understanding around the uranium mineralization and the rock-forming minerals of the hosted granitic rocks, to facilitate the choice of the appropriate ore-processing techniques, it was necessary to identify the mineral composition and the radiometric specifications of the used granitic rock. The synthesized adsorbents revealed a promising selective adsorption toward the U(VI) ions from its bearing solutions even with the competence of other cations.

     

Sorption mechanism of U(VI) on a reference montmorillonite: Binding to the internal and external surfaces

Batch type experiments of U(VI) sorption on a reference montmorillonite(SWy-2) were carried out over wide ranges of pH, ionic strength, and totalU(VI) concentration. The influences of these factors on the sorption behaviorof U(VI) were analyzed to gain a macroscopic understanding of the sorptionmechanism. The sorption of U(VI) on montmorillonite showed a distinct dependencyon ionic strength. When it was low (0.01 or 0.001M), almost all of the totalU(VI) was sorbed over the whole pH range studied, therefore, the dependencyon pH was not clear. But the sorption of U(VI) on montmorillonite showed asorption pH edge in the high ionic strength condition (0.1M), like those onother clay minerals, kaolinite and chlorite. A mechanistic model was establishedby considering the mineral structure of montmorillonite together with ourprevious EPR result, which successfully explained the U(VI) sorption on montmorilloniteover the whole range of experimental conditions. The model describes the U(VI)sorption on montmorillonite as simultaneous and competitive reactions of ionexchange and surface complexation, whose relative contribution to the totalsorption depends on pH and ionic strength. At low ionic strength and low pHconditions, ion exchange was the dominant mechanism for U(VI) sorption onmontmorillonite. At high ionic strength and high pH conditions, surface complexationwas the dominant     

An EXAFS and TRLFS investigation on uranium(VI) sorption to pristine and leached albite surfaces

Uranium(VI) was sorbed to freshly ground and leached albite in batch and flow-through systems in the pH range 5.0-6.4. The uranium(VI) surface complexes were studied by extended X-ray absorption fine structure (EXAFS) spectroscopy and time-resolved laser-induced fluorescence spectroscopy (TRLFS). The EXAFS analysis of uranium(VI) sorbed on albite at pH 5.8 and 5 x 10(-6) M U(VI) showed one silicon atom at a USi distance of 3.09 A, which is indicative of the formation of an inner-sphere, mononuclear, bidentate uranium(VI) surface complex, Si(O)2UO2, on the silicate tetrahedra of albite. Two additional uranium(VI) sorption complexes were detected by TRLFS at higher initial aqueous U(VI) concentrations. However, the structure of these surface complexes could not be derived from EXAFS, since the measured EXAFS spectra represent the average of two surface complex structures. In order to simulate U(VI) sorption onto weathered feldspar surfaces, albite was leached with 0.01 M HClO4, resulting in surface material similar to amorphous silica gel. EXAFS showed that the equatorial oxygen shell of uranium(VI) sorbed on this material at pH 5.0 and 5.8 was split in two distances of 2.23 and 2.44 A. This indicates the formation of an inner-sphere surface complex.     

Regularities of the sorption behavior of actinide ions on mineral colloid particles

It is shown that an alternative to K _d in describing sorption at low degrees of surface saturation of colloid particles is pH₅₀ which takes into account both the properties of the sorbent and sorbate. The correlations of pH₅₀ with cation charge density for the An(III)-An(IV)-An(V)-An(VI) series and with hydrolysis constants are presented. The redox reactions with plutonium that accompany its sorption onto Fe(III) oxides are discussed.     

U(VI) sorption on kaolinite: effects of pH,U(VI) concentration and oxyanions

U(VI) sorption on kaolinite was studied as functions of contact time, pH, U(VI) concentration, solid-to-liquid ratio (m/V) by using a batch experimental method. The effects of sulfate and phosphate on U(VI) sorption were also investigated. It was found that the sorption kinetics of U(VI) can be described by a pseudo-second-order model. Potentiometric titrations at variable ionic strengths indicated that the titration curves of kaolinite were not sensitive to ionic strength, and that the pH of the zero net proton charge (pH_PZNPC) was at 6.9. The sorption of U(VI) on kaolinite increased with pH up to 6.5 and reached a plateau at pH >6.5. The presence of phosphate strongly increased U(VI) sorption especially at pH <5.5, which may be due to formation of ternary surface complexes involving phosphate. In contrast, the presence of sulfate did not cause any apparent effect on U(VI) sorption. A double layer model was used to interpret both results of potentiometric titrations and U(VI) sorption on kaolinite.     

Adsorption of U(VI) onto the carboxymethylated chitosan/Na-bentonite membranes: kinetic,isothermic and thermodynamic studies

The carboxymethylated chitosan (CMC)/Na-bentonite (Na-Bt) composite membranes were prepared and throughly characterized. The Na-Bt/CMC mass ratio was optimized, and CB10 (membrane with Na-Bt/CMC mass ratio of 10%) was selected as the best membrane for U(VI) sorption. XPS analysis indicates that the main mechanism for UO₂²⁺ sorption onto CB10 is through inner-surface complexation. The sorption kinetics followed pseudo-second order model, indicating the chemisorption as the rate-controlling step. The U(VI) sorption on CB10 is endothermic and spontaneous, with the maximum mono-layer adsorption capacity of 115.6 mg/g at pH 5.0 and 298 K. Finally, the U(VI)-loaded CB10 can consecutively desorbed and reused for several cycles.     

Sorption kinetic studies of U(VI) on inorganic and organic modified red earth: comparison of linear and non-linear methods

The sorption of U(VI) on natural red earth, inorganic modified red earth and organic modified red earth were studied under given conditions. Kinetic studies of U(VI) sorption onto the red earth samples were discussed by linear and non-linear approaches. The results indicated that the inorganic modification greatly improved the surface properties and the sorption kinetics characteristics, and that organic modification increased the sorption capacity significantly. The non-linear pseudo-second-order kinetic model could fit the kinetics much better compared with the other linear forms.

     

Removal of U(VI) from aqueous solutions by using MWCNTs and chitosan modified MWCNTs

In this paper, the multiwalled carbon nanotubes (MWCNTs) were modified with chitosan (CS) by using low temperature plasma grafting technique (denoted as MWCNT-CS). The prepared MWCNTs and MWCNT-CS were characterized by SEM, TEM, FTIR and Raman spectroscopy in detail and the results suggested that CS molecules were successfully grafted on the surfaces of MWCNTs. The materials were applied as adsorbents in the removal of U(VI) ions from large volumes of aqueous solutions as a function of environmental conditions. The removal of U(VI) from aqueous solution to MWCNTs and MWCNT-CS increased with increasing pH values at pH < 7, and then decreased with increasing pH values at pH > 7. The sorption of U(VI) on MWCNTs and MWCNT-CS was strongly dependent on pH and independent of ionic strength. The sorption of U(VI) on MWCNTs and MWCNT-CS was dominated by inner-sphere surface complexation rather than by ion exchange or outer-sphere surface complexation. The surface grafted chitosan molecules can enhances U(VI) sorption on MWCNTs obviously, which was also evidenced from the XPS spectroscopy analysis. The results of high sorption capacity of U(VI) on MWCNT-CS suggest that the MWCNT-CS nanomaterial is a suitable candidate in the preconcentration of U(VI) ions from large volumes of aqueous solutions.     

Thermodynamic parameters and sorption of U(VI) on ACSD

This paper discusses the sorption properties for U(VI) by alginate coated CaSO₄·2H₂O sepiolite and calcined diatomite earth (Kieselguhr) (ACSD). The removal of U(VI) from aqueous solution by sorption onto ACSF in a single component system with various contact times, pH, temperatures, and initial concentrations of U(VI) was investigated. The sorption patterns of uranium on the composite adsorbent followed the Langmuir, Freundlich and Dubinin-Radushkhevic (D-R) isotherms. The Freundlich, Langmuir, and D-R models have been applied and the data correlated well with Freundlich model and that the sorption was physical in nature (sorption energy, E _a = 17.05 kJ/mol). The thermodynamic parameters such as variation of enthalpy ΔH, variation of entropy ΔS and variation of Gibbs free energy ΔG were calculated from the slope and intercept of lnK ₀ vs. 1/T plots. Thermodynamic parameters (ΔH _ads = 31.83 kJ/mol, ΔS _ads = 167 J/mol·K, ΔG ^o _ads (293.15 K) = −17.94 kJ/mol) showed the endothermic heat of sorption and the feasibility of the process. The thermodynamics of U(VI) ion/ACSD system indicates the spontaneous and endothermic nature of the process. It was noted that an increase in temperature resulted in a higher uranium loading per unit weight of the adsorbent.     

Surface modification to improve the sorption property of U(VI) on mesoporous silica

Polyoxometalates K₇[α-PW₁₁O₃₉]·14H₂O (PW11) modified mesoporous silica (MCM-48) with cubic structure, was prepared by impregnation and calcination methods. The modified mesoporous silica sorbent (PW11/MCM-48) was studied as a potential adsorbent for U(VI) from aqueous solutions. MCM-48 and PW11/MCM-48 were confirmed by X-ray diffraction and nitrogen physisorption techniques. The results indicate the original keggin structure of PW11 and mesoporous structure of MCM-48 are maintained after supporting PW11 on mesoporous silica MCM-48. The effects of contact time, solid-to-liquid ratio (m/V), solution pH and ionic strength on U(VI) sorption behaviors of the pure and modified mesoporous silicas were also studied. Typical sorption isotherms such as Langmuir and Freundlich isotherms were determined for sorption process. The results suggest that the sorption of U(VI) on MCM-48 or PW11/MCM-48 are strongly dependent on pH values but independent of ionic strength. The sorption capacity of PW11/MCM-48 for U(VI) is about ten times more than that of MCM-48.     

Application of NKF-6 zeolite for the removal of U(VI) from aqueous solution

To better understand the application of NKF-6 zeolite as an adsorbent for the removal of U(VI) from radionuclides and heavy metal ions polluted water, herein, NKF-6 zeolite was employed to remove U(VI) at different experimental conditions. The influence of solid/liquid ratio, contact time, pH, ionic strength, humic substances and temperature on sorption of U(VI) to NKF-6 zeolite was investigated using batch technique under ambient conditions. The experimental results demonstrated that the sorption of U(VI) on NKF-6 zeolite was strongly dependent on pH. The sorption property of U(VI) was influenced by ionic strength at pH < 7.0, whereas was independent of ionic strength at pH > 7.0. The presence of fulvic acid or humic acid promoted the sorption of U(VI) on NKF-6 zeolite at low pH values while restrained the sorption at high pH values. The thermodynamic parameters (i.e., ΔS ⁰, ΔH ⁰, and ΔG ⁰) calculated from the temperature-dependent sorption isotherms demonstrated that the sorption process of U(VI) on NKF-6 zeolite was endothermic and spontaneous. At low pH values, the sorption of U(VI) was dominated by outer-sphere surface complexation and ion exchange with Na⁺/H⁺ on NKF-6 zeolite surfaces, while inner-sphere surface complexation was the main sorption mechanism at high pH values. From the experimental results, one can conclude that NKF-6 zeolite can be used as a potential adsorbent for the preconcentration and solidification of U(VI) from large volumes of aqueous solutions.