Sorption of 60Co(II) from aqueous solutions onto biosynthesized zinc oxide nanocomposites

Journal of Radioanalytical and Nuclear Chemistry - Nano ZnO is biosynthesized using Lactobcillus sp. Poly Acrylic acid-co-Acrylonitrile/ZnO, PAACAN/ZnO, and poly Acrylic acid-co-Maleic acid/ZnO,...     

Sorption of Sr(II) and Eu(III) onto pyrite under different redox potential conditions

Understanding sorption processes is fundamental for the prediction of radionuclide migration in the surroundings of a deep geological disposal of high-level nuclear wastes. Pyrite (FeS2) is a mineral phase often present as inclusions in temperate soils. Moreover, it constitutes an indirect corrosion product of steel, a containment material that is candidate to confine radionuclides in deep geological disposals. The present study was thus initiated to determine the capacity of pyrite to immobilize Sr(II) and Eu(III). An air oxidized pyrite and a freshly acid-washed (non-oxidized) pyrite were used in background electrolytes of varying reducing-oxidizing ability (NaCl, NH3OHCl, and NaClO4) to study the sorption of both cationic species. The sorptive capacity of pyrite appeared directly correlated to the oxidation of the surface. Non-oxidized pyrite had nearly no affinity for the studied cations whereas Sr(II) and Eu(III) species were significantly retained by oxidized pyrite surface. Using the surface complexation theory, sorption mechanisms were modeled with the Fiteql v3.2 and the Jchess 2.0 codes. Sorption of both Sr and Eu was well fitted, assuming hydroxylated species as the major surface species. This study demonstrates that not only the components of a barrier but also the redox conditions and specifications should be well characterized to predict transport of contaminants in the surrounding of a nuclear wastes disposal.     

Modelling of the Sorption of Sr(II) on Hydrous Zirconium Oxide

The amphoteric acid-base behavior of hydrous zirconium oxide (HZO) was investigated by titrating HZO with 0.05M HNO₃ and NaOH at constant ionic strength. The sorption of strontium from 0.05M NaNO₃ solution was measured as a function of pH. Abrupt increase in sorption was observed at the equilibrium pH of 9. The experimental titration and strontium sorption data on HZO were evaluated using the constant capacitance model (CCM) and diffuse double layer model (DLM). Various model parameters of Surface Complexation Models (SCM) were estimated, numerically, by non-linear regression. Modeling the sorption and speciation of Sr²⁺ on HZO indicated that the hydrolysis of Sr²⁺ to lower charged SrOH⁺ is the pre-requisite for the abrupt sorption behavior at pH 9.     

Sorption of Cu(II) onto vineyard soils: macroscopic and spectroscopic investigations

The sorption of Cu on five vineyard soils was examined via macroscopic and spectroscopic investigations. The composition of the soils was previously determined using X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). X-ray absorption spectroscopy (XAS) was employed to determine the metal environment with regard to the identity and interaction of the nearest atomic neighbors, the bond distances, and the coordination numbers. The five soils present similar sorption properties and there is no XAS evidence that the nature of the soil samples affects the local chemical environment of Cu(II). The kinetics of the Cu sorption reactions is rapid, with the equilibrium loading of Cu on the surface achieving approximately 200 mumol g(-1), i.e., 12.7 mg g(-1). The XAS data indicate that Cu is adsorbed in the form of inner-sphere complexes with first shell CuO parameters of four equatorial CuO bonds equal to 1.93 A and two axial CuO bonds at 2.43 A. This is in accordance with a Jahn-Teller distorted octahedron environment around copper. Our results provide evidence of the complexation of Cu(II) onto soil organic matter coated with an inorganic surface (quartz, clay, and goethite).     

Sorption behavior of 85Sr onto manganese oxides with tunnel structure

Journal of Radioanalytical and Nuclear Chemistry - Sorption behavior of strontium ions on manganese oxides obtained by sol–gel technique reduction of KMnO4 by different reagents (H2O2, MnCl2...     

Sorption of Pu(VI) onto TiO2

The sorption of Pu(VI) onto TiO(2) was studied as a function of pH (2-10) and Pu concentration (10(-8)-10(-4) M) under an N(2) atmosphere, in 0.016 and 0.1 M NaClO(4). A batch-wise method was used, in which pH was measured in separate experimental containers after removal of a sample to determine the amount of Pu that had been sorbed. As Pu is radioactive, it was used as a tracer and measured by liquid scintillation counting. No ionic strength dependence was discerned, which was taken as an indication of inner sphere complex formation. In the interval of pH 2-7 the system could be described by the formation of two positively charged surface complexes using a 1-pK Stern model. Sorption of the plutonyl ion (PuO(2)(2+)) and the first hydrolysis species (PuO(2)(OH)(+)) was estimated using FITEQL to logK(1)=6.9 and logK(2)=1.4, respectively.     

Sorption behavior of Sn(II) onto Haro river sand from aqueous acidic solutions

The sorption behavior of Sn(II) onto Haro river sand has been examined with respect to nature of electrolyte, agitation time, dosage of sorbent and concentration of sorbate. Maximum sorption (95.5%) has been achieved from 0.034M hydrochloric acid solution after equilibrating sorbate (2·10⁻⁵M) and sorbent (50 mg) for 120 minutes at aV/W ratio of 90 cm³·g⁻¹. The kinetic data have been subjected to Morris-Weber and Lagergren equations. The kinetics of sorption proceeds a two stage process consisting of a relatively slow initial uptake followed by a much rapid increase in the sorption. The rate constant of intraparticle transport, K_d, comes out to be 8.75·10⁻⁸ mol·g⁻¹·min^−1/2 and the first order rate constant for sorption is 0.0416 min⁻¹. The sorption data of Sn(II) onto Haro river sand followed Langmuir, Freundlich and Dubinin-Radushkevich (D-R) type isotherms. The Langmuir constant,Q, related to sorption capacity and,b, related to sorption energy are computed to be 10.6±1.1 μmol·g⁻¹ and 1123±137 dm³·mol⁻¹, respectively. The D-R isotherm yields the values ofC _m=348±151 μmol·g⁻¹ and β=−0.01044±0.0008 mol²·kJ⁻² and ofE=6.9±0.3 kJ·mol⁻¹. In all three isotherms correlation factor (γ) is ≥0.99. The influence of common anions and cations on the sorption has been investigated. Zn(II), Mg(II), oxalate, Pb(II), Mn(II) and tartrate reduce the sorption significantly whereas Fe(II) causes substantial increase in the sorption. It is essential that all ions causing a decrease in the sorption of Sn(II) must be absent from the sorptive solution otherwise low sorption yields would result.     

Sorption behavior of Am(III) onto granite

Sorption behavior of Am(III) onto granite was investigated. The distribution coefficient (K _d ) of Am(III) onto granite was determined in the solution of which pH was ranged from 2.9 to 11.4 and ionic strength was set at 10⁻² and 10⁻¹. TheK _d values were found to increase with increasing pH and with decreasing ionic strength. The obtained data were successfully analyzed by applying an electrical double layer model. The optimum parameter values of the double layer electrostatics and adsorption reactions were obtained, and the selective adsorption behavior of Am(III) onto the granite was discussed.     

Sorption characteristics of Am(III), Sr(II) and Cs(I) on bentonite and granite

The ability of the back-fill and the host rock materials to take up radioisotopes like ²⁴¹Am, ^85,89Sr and ¹³⁷Cs has been examined as a function of contact time, pH, amount of sorbent, sorbate concentration, and the presence of complementary cations. A batch technique using actual borehole water from the granite formation has been utilized. In general, the uptake of nuclides by bentonite is much higher than that with granite. The sorption order of nuclides on bentonite is Am>Cs>Sr. The presence of complementary cations, Na⁺, K⁺, Ca²⁺ and Mg²⁺ depresses the sorption of Cs and Sr on bentonite. The sorption data have been interpreted in terms of Freundlich and Langmuir isotherm equations. Utilizing the Langmuir isotherm equation, the monolayer capacity, V _m ,and the binding constant, K, have been evaluated. The change in free energy for the sorption of nuclides on bentonite has also been calculated.     

Sorption speciation of nickel(II) onto Ca-montmorillonite: batch, EXAFS techniques and modeling

The sorption speciation of Ni(II) on Ca-montmorillonite was evaluated using a combination of batch experiments, extended X-ray absorption fine structure (EXAFS) spectroscopy and modeling. The pH and temperature at the aqueous-montmorillonite interface affects both the extent of Ni(II) sorption as well as the local atomic structure of the adsorbed Ni(II) ions. At 0.001 mol L(-1) Ca(NO(3))(2) and low pH, the study reveals that the majority of Ni(II) is adsorbed in the interlayers of Ca-montmorillonite coordinated by six water molecules in an octahedron as an outer-sphere complex. At higher pH, inner-sphere surface complexes are formed. The Ni-Si/Al distances (R(Ni-Al) = 3.00 ?, R(Ni-Si1) = 3.10 ? and R(Ni-Si2) = 3.26 ?) determined by EXAFS confirm the formation of mononuclear complexes located at the edges of Ca-montmorillonite platelets at pH 7.5 and 8.5. At pH 10.0, the Ni-Ni/Si distances (R(Ni-Ni) = 3.07 ? and R(Ni-Si) = 3.26 ?) indicates the formation of Ni-phyllosilicate precipitates. A rise in temperature promotes inner-sphere complexation, which in turn leads to an increase in Ni(II) sorption on Ca-montmorillonite. Sorption edges are fitted excellently by surface complexation model (SCM) with the aid of surface species determined from EXAFS spectroscopy.     

Kinetics and Equilibrium Models for Sorption of Cu(II) onto a Novel Manganese Nano-adsorbent

The studies of kinetics and equilibrium sorption of Cu(II) were undertaken using nanoscale zerovalent manganese (nZVMn) synthesized by chemical reduction in a single pot system. nZVMn was characterized using scanning electron microscopy, energy dispersive x-ray, and surface area determined by Brunauer–Emmett–Teller. The effect of pH, contact time, adsorbent dose, agitation speed, initial Cu(II) concentrations, temperature, and ionic strength on the sorption of Cu(II) onto nZVMn were investigated in a batch system. The kinetic data followed pseudo-second-order. The mechanism was governed by pore diffusion. The equilibrium sorption data were tested by Freundlich, Langmuir, Temkin, Dubinin–Kaganer–Raduskevich, and Halsey isotherm models. The Langmuir monolayer adsorption capacity (Q_max = 181.818 mg/g) is much greater compared to other nano-adsorbents used in sorption of Cu(II). The thermodynamic parameters (ΔH⁰, ΔS⁰, ΔG⁰) revealed a feasible, spontaneous, and endothermic adsorption process. nZVMn has a great potential for effective removal of copper (II) in aqueous solution.     

Sorption behavior of thorium(IV) onto activated bentonite

Journal of Radioanalytical and Nuclear Chemistry - Activated bentonite was obtained from acid activation and purification of raw bentonite, sorption of Th(IV) onto activated bentonite was studied...     

Spectroscopic Study of Cm(III) Sorption onto gamma-Alumina

The surface sorption of Cm(III) onto aqueous suspensions of alumina is investigated by time-resolved laser fluorescence spectroscopy (TRLFS). The experiment is performed under an Ar atmosphere at an ionic strength of 0.1 M NaClO(4). The pH is varied between 2 and 10 and the metal ion concentration between 2.7x10(-8) and 4.5x10(-5) mol/L. With increasing pH, two Cm(III)-alumina surface species are identified which are attributed to identical withAl-O-Cm(2+)(H(2)O)(5) and identical withAl-O-Cm(+)(OH)(H(2)O)(4). The two curium-alumina surface complexes are characterized by their emission spectra (peak maxima at 601.2 nm and 603.3 nm, respectively) and fluorescence emission lifetime (both 110&mgr;s). In the concentration range investigated, the surface complex formation is not dependent on the metal ion concentration but only on the pH. Additionally, the concentration ratio of the two surface species is found to be independent of the metal ion concentration. No spectroscopic evidence for the presence of "strong" and "weak" sites can be found at different surface coverages. Copyright 2001 Academic Press.     

Surface complexation modeling of Sr(II) and Eu(III) adsorption onto oxidized multiwall carbon nanotubes

Acid-base titrations of oxidized multiwall carbon nanotubes (MWCNTs), Sr(II) and Eu(III) adsorptions onto oxidized MWCNTs were conducted to investigate the surface charge characteristics of oxidized MWCNTs and the surface complexation interactions between Sr(II)/Eu(III) and oxidized MWCNTs. The results suggested that Sr(II) and Eu(III) adsorptions onto oxidized MWCNTs increased with increasing pH, and decreased with increasing ionic strength, and the affinity of oxidized MWCNTs for Eu(III) was much higher than that for Sr(II). The diffuse layer model (DLM) fitted the experimental data of Sr(II) and Eu(III) adsorptions well with the aid of FITEQL 3.2.     

Sorption of uranium from alkaline waste onto radiation grafted phosphoryl-g-Teflon matrix

High energy ⁶⁰Co γ-radiation was used to graft glycidylmethacrylate onto Teflon scrap through mutual radiation grafting technique. The epoxy ring of grafted polyGMA chains were later converted to U selective phosphoryl group, chemically. The grafted matrix was used as solid–liquid adsorbent of uranium from alkaline waste solution. More than 98% recovery of uranium from alkaline waste (~pH 8) solution was achieved. The effect of grafting extent on adsorption kinetics was also investigated. The selectivity of uranium extraction over other fission products was established. The uptake of other fission products was <5% for equilibration time of ~1 h.

     

Sorption and thermodynamic behavior of zinc(II)-thiocyanate complexes onto polyurethane foam from acidic solutions

The uptake of Zn(II)-SCN complex onto polyurethane foam (PUF) has been investigated in detail with respect to different composition and variable concentration of electrolyte, zinc, thiocyanate ions and PUF, and equilibration time. The sorption data followed both Langmuir and Dubinin-Radushkevich (D-R) sorption isotherms over the entire concentration range of zinc investigated whereas Freundlich sorption isotherm is obeyed upto 13.6^.10^-3M concentration. The Langmuir constants Q = 202±7 mmole^.g^-1 and of b = (1.78±0.31.10⁴ dm^3.mole^-1 and of D-R paraneter X _m = 493±1 mmole^.g^-1, b = activity coefficient = -0.028±0.0002 and of sorption energy E = 13.2±0.5 kJ^.mole^-1 and Freundlich constants 1/n = 0.42±0.03 and c _m = 6.47±1.7 mmole^.g^-1 were evaluated. The influence of temperature variation on sorption have yielded DH = -77.5±2.9 kJ^.mole^-1, DS = -5±0.09 J^.mole^-1.K^-1 and DG = -6.67±0.05 kJ^.mole^-1. The effect of common anions and cations on the sorption has been examined. Sulphate, ascorbate and bromide ions enhances the sorption to some extent whereas nitrite, Pb(II), Fe(III), Al(III), Cu(II) and Co(II) decrease to sorption significantly. A possible mechanism has been envisaged for Zn(II)-SCN sorption onto PUF.     

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.     

Measurement and Modeling of Th Sorption onto TiO(2)

The sorption and desorption of Th onto TiO₂ (10 g/L) was studied as a function of pH (1–11), ionic strength (0.005–0.1 M NaCl, NaClO₄), thorium concentration (from 1 × 10⁻⁹ to 3 × 10⁻² M), and carbonate concentration (up to 10⁻² M) using ²³⁴Th tracer. The results indicate the reversible formation of an inner sphere complex with a strong pH dependence. No effect of the carbonate on sorption could be measured in the pH range investigated (5–10.5). The data were fitted with five different conceptual models (constant capacitance, diffuse layer, Stern, triple layer, and a nonelectrostatic model) using FITEQL. Different hydroxy complex surface reactions were tried, one at a time, varying the site density (1–12 sites/nm²). The reaction that provided the best fit depended strongly on the surface site density and the model used. To be able to fit a reaction to the pH-dependent data with the compact layer models, the effect of the electrostatic term had to be decreased by decreasing the site density below 5 sites/nm². None of the electrostatic models could be used to fit all of the isotherm data. The nonelectrostatic model could be used to reasonably fit both the pH-dependent and isotherm data.     

Copper(II) complex intercalated graphene oxide nanocomposites as versatile,reusable catalysts for click reaction

In this work, we report the efficient, high stable copper(II) complexes intercalated graphene oxide (GO) used as green catalysts for copper(II) complex mediated click reaction. Copper(II) Bis(2,2′-bipyridine) [Cu^II (bpy)₂] (C1) and Copper(II) Bis(1,10-phenanthroline) [Cu^II (phen)₂] (C2) have synthesized for the intercalation of corresponding nanocomposites with GO, [GO@Cu^II (bpy)₂] (GO-C1) and [GO@Cu^II (phen)₂] (GO-C2). The noncovalent interaction of complexes supported on the surface of the GO nanosheets proves as an evident active site to facilitate the enhanced catalytic activity of copper-catalyzed alkyne azide cycloaddition (Cu^IIAAC) reaction for the isolation of 1,4-disubstituted-1,2,3-triazoles as click products in shorter reaction time with 80%–91% yield (five examples). The X-ray diffraction (XRD) pattern of these composites shows the enhanced interlayers d-spacing range of 1.01–1.12 nm due to the intercalation of copper(II) complexes in between the GO basal planes and characterized by X-ray photoelectron spectroscopy (XPS), Fourier-transform infrared spectroscopy (FT-IR), Raman, UV, scanning electron microscope (SEM), and thermogravimetric analysis (TGA). The as-prepared nanocomposites were employed for the typical click reactions using the substrates of azide and acetylene. These classes of composite materials can be referred to recyclable, heterogeneous, green catalysts with high atom economy and could also be used for the isolation of click products in biomolecules.