Investigation of radionuclide ^(60)Co(Ⅱ) binding to TiO_2 by batch technique,surface complexation model and DFT calculations

The interaction between radionuclides and solid/water interfaces is important to understand the physicochemical processes of radionuclides in the natural environment.Herein,the interaction of 60Co(Ⅱ) with TiO 2 in aqueous solution as a function of pH and ionic strength was studied by using batch technique combined with surface complexation model and density functional theory(DFT) calculations.The batch experimental results showed that the adsorption of 60Co(Ⅱ) was dependent on pH and independent of ionic strength,indicating the formation of inner-sphere surface complexes on TiO 2 surfaces.The results of surface complexation models and DFT calculations indicated that the surface species of 60Co(Ⅱ) adsorbed on TiO 2 followed the trend:B structure(i.e.,60Co(Ⅱ) was linked to one bridge oxygen site) was the dominant surface species at low pH,and TT structure(i.e.,60Co(Ⅱ) was linked to two terminal oxygen sites) became the important surface complex at neutral and alkaline pH values.These results demonstrated that a multi-technique approach could lead to definitive information on the structures of adsorbed 60Co(Ⅱ) at the molecular level at the TiO 2 /water interfaces,as well as realistic models to rationalize and accurately evaluate the macroscopic manifestations of radionuclide adsorption phenomena.

Heavy metal adsorption on the Le An River sediment —The adsorption model

In this study,the surface properties and adsorption properties of the Le An River sedi- ment were modelled via surface complexation approach.The model parameters were determined based on the data of our potentiometric titration experiments and the metal adsorption experiments with the Le An River sediment samples.Consequently,the surface complexation models for the natural sediment,in our case the Le An River sediments,which can interpret the experimental data very well were successfully established.Three typical surface complexation models that is the con- stant capacitance model,the diffuse layer model and the triple layer model,were considered in this research.This work indicated that the consistency and the interdependency among model parame- ters together with the selection of the surface adsorbed species should be emphasized.

The sorption mechanisms of Th(Ⅳ) on attapulgite

The surface properties of intrinsic and activated attapulgite were studied using potentiometric titration. The sorption mechanisms of Th（IV） on intrinsic and activated attapulgite were investigated by employing surface complexation model and FITEQL 3.2 code. The results indicated that the sorption sites of intrinsic attapulgite involved in the sorption process were main ion exchange site （ ≡ XNa/K）, strong site （≡ SsOH） and weak site （ ≡ SwOH）, while only strong site （ ≡SSOH） and weak site （≡SwOH） were predominant for activated attapulgite. At pH 〈 2.5, the species of Th（IV） was main Th4＋ in aqueous solution; then the hydrolysis species of Th（IV） （i.e., Th（OH）22＋, Th（OH）3＋ and Yh（OH）40） gradually formed as pH increasing. For the sorption of Th（IV） on intrinsic attapulgite, both ion exchange species （ ≡ X2Th） and inner-sphere surface complexes （ ≡ SsOTh） were dominant, while only inner-sphere surface complexes （i.e., ≡SSOThOH and ≡ SWOTh） were observed for Th（IV） sorption to activated attapulgite. In the presence of humic acid （HA）, the sorption of Th（IV） on activated attapulgite was obviously enhanced; and both ≡ SsOH-HA-Th and≡ SSOTh were the predominant speciation. It was also interesting to find that the addition of HA obviously provoked the desorption behavior of Th（IV）.

Probing and understanding interaction of Eu(Ⅲ)withγ-alumina in presenceof malonic acid

Radionuclide migration in aquatic environment is influenced by its sorption onto colloids/mineral oxides and the presence of organic complexing anions.With a view to understand the sorption of trivalent actinides by mineral oxides in presence of organic acid,in the present study,Eu(Ⅲ),malonic acid(MA)andγ-alumina are considered as representatives of trivalent actinides,low molecular weight natural occurring organic acid and aluminol sites,respectively.The influence of MA on sorption of Eu(Ⅲ)byγ-alumina was elucidated by batch sorption,spectroscopic techniques and surface complexation modeling,for the first time.Attenuated Total Reflection-Fourier Transform Infrared spectroscopic studies of MA sorbed onγ-alumina revealed the presence of two inner-sphere surface complexes.Batch sorption for binary(alumina-Eu(Ⅲ))and ternary(alumina-Eu(Ⅲ)-MA)systems were investigated as a function of p H,Eu(Ⅲ)concentration and sequential addition of Eu(Ⅲ)/MA.The p H edge for Eu(Ⅲ)sorption shifts to higher p H with increasing Eu(Ⅲ)concentration.In ternary systems,Eu(Ⅲ)sorption is significantly enhanced at p H<4.5.Eu(Ⅲ)speciation onγ-alumina is independent of addition sequence of Eu(Ⅲ)/MA.Time resolved fluorescence spectroscopy of Eu(Ⅲ)sorbed onγ-alumina exhibited two surface species,≡XOEu^2+and(≡YO)2 Eu^(+).The enhancement in I 616/I 592 and lifetime for ternary systems,as compared to binary system,at low p H,indicates the participation of Eu-MA complexes in the formation of surface species in ternary systems.The diffuse layer model has been employed to successfully model the experimental sorption profiles of binary and ternary systems,using code FITEQL 4.0,by considering the surface species identified by spectroscopic techniques.

Adsorption performance and physicochemical mechanism of MnO_(2)-polyethylenimine-tannic acid composites for the removal of Cu(Ⅱ) and Cr(Ⅵ) from aqueous solution

In this work,an adsorbent,which we call MnPT,was prepared by combining MnO_(2),polyethylenimine and tannic acid,and exhibited efficient performance for Cu(Ⅱ) and Cr(VI) removal from aqueous solution.The oxygen/nitrogen-containing functional groups on the surface of MnPT might increase the enrichment of metal ions by complexation.The maximum adsorption capacities of MnPT for Cu(Ⅱ) and Cr(Ⅵ) were 121.5 and 790.2 mg·g^(-1),respectively.The surface complexation formation model was used to elucidate the physicochemical interplay in the process of Cu(Ⅱ) and Cr(Ⅵ) co-adsorption on MnPT.Electrostatic force,solvation action,adsorbate-adsorbate lateral interaction,and complexation were involved in the spontaneous adsorption process.Physical electrostatic action was dominant in the initial stage,whereas chemical action was the driving force leading to adsorption equilibrium.It should be noted that after adsorption on the surface of MnPT,Cr(Ⅵ) reacted with some reducing functional groups(hydroxylamine-NH_(2))and was converted into Cr(Ⅲ).The adsorption capacity declined by 12% after recycling five times.Understanding the adsorption mechanism might provide a technical basis for the procedural design of heavy metal adsorbents.This MnPT nanocomposite has been proven to be a low-cost,efficient,and promising adsorbent for removing heavy metal ions from wastewater.