The effects of pH,contact time and natural organic ligands on radionuclide Eu(Ⅲ) adsorption and mechanism on titanate nanotubes(TNTs) are studied by a combination of batch and extended X-ray absorption fine structure...The effects of pH,contact time and natural organic ligands on radionuclide Eu(Ⅲ) adsorption and mechanism on titanate nanotubes(TNTs) are studied by a combination of batch and extended X-ray absorption fine structure(EXAFS) techniques.Macroscopic measurements show that the adsorption is ionic strength dependent at pH < 6.0,but ionic strength independent at pH > 6.0.The presence of humic acid(HA) /fulvic acid(FA) increases Eu(Ⅲ) adsorption on TNTs at low pH,but reduces Eu(Ⅲ) adsorption at high pH.The results of EXAFS analysis indicate that Eu(Ⅲ) adsorption on TNTs is dominated by outer-sphere surface complexation at pH < 6.0,whereas by inner-sphere surface complexation at pH > 6.0.At pH < 6.0,Eu(Ⅲ) consists of ～ 9 O atoms at REu?O ≈ 2.40 in the first coordination sphere,and a decrease in NEu-O with increasing pH indicates the introduction of more asymmetry in the first sphere of adsorbed Eu(Ⅲ).At long contact time or high pH values,the Eu(Ⅲ) consists of ～2 Eu at REu-Eu ≈ 3.60 and ～ 1 Ti at REu-Ti ≈ 4.40 ,indicating the formation of inner-sphere surface complexation,surface precipitation or surface polymers.Surface adsorbed HA/FA on TNTs modifies the species of adsorbed Eu(Ⅲ) as well as the local atomic structures of adsorbed Eu(Ⅲ) on HA/FA-TNT hybrids.Adsorbed Eu(Ⅲ) on HA/FA-TNT hybrids forms both ligand-bridging ternary surface complexes(Eu-HA/FA-TNTs) as well as surface complexes in which Eu(Ⅲ) remains directly bound to TNT surface hydroxyl groups(i.e.,binary Eu-TNTs or Eu-bridging ternary surface complexes(HA/FA-Eu-TNTs)).The findings in this work are important to describe Eu(Ⅲ) interaction with nanomaterials at molecular level and will help to improve the understanding of Eu(Ⅲ) physicochemical behavior in the natural environment.展开更多
Humic substances(HS) substantially affect heavy metal(M) adsorption on mineral surfaces. However, quantitative descriptions of ternary systems involving M, HS and mineral surfaces remain unclear. This study examines a...Humic substances(HS) substantially affect heavy metal(M) adsorption on mineral surfaces. However, quantitative descriptions of ternary systems involving M, HS and mineral surfaces remain unclear. This study examines adsorption in a model ternary system including Eu(III), fulvic acid(FA) and silica, and describes the adsorption of Eu(III) and FA by combining a double-layer model(DLM) and the Stockholm humic model(SHM). SHM explains the binding of H+ and Eu3+ to FA and the DLM for FA and Eu(III) adsorption on silica. Experimental results showed that the presence of FA promotes Eu(III) adsorption at acidic pH values, but decreases it at basic pH values, which indicates the formation of ternary surface complexes. Modeling calculations have shown that two ternary surface complexes are required to describe the experimental results in which Eu3+ acts as a bridge between the surface site and FA. The present study suggests that the discrete-site approach to HS is a promising method for interpreting the adsorption data for M, HS and mineral ternary systems.展开更多
基金supported by the National Natural Science Foundation of China(20907055,20971126 & 21077107)the National Basic Research Program of China(2007CB936602 & 2011CB933700)
文摘The effects of pH,contact time and natural organic ligands on radionuclide Eu(Ⅲ) adsorption and mechanism on titanate nanotubes(TNTs) are studied by a combination of batch and extended X-ray absorption fine structure(EXAFS) techniques.Macroscopic measurements show that the adsorption is ionic strength dependent at pH < 6.0,but ionic strength independent at pH > 6.0.The presence of humic acid(HA) /fulvic acid(FA) increases Eu(Ⅲ) adsorption on TNTs at low pH,but reduces Eu(Ⅲ) adsorption at high pH.The results of EXAFS analysis indicate that Eu(Ⅲ) adsorption on TNTs is dominated by outer-sphere surface complexation at pH < 6.0,whereas by inner-sphere surface complexation at pH > 6.0.At pH < 6.0,Eu(Ⅲ) consists of ～ 9 O atoms at REu?O ≈ 2.40 in the first coordination sphere,and a decrease in NEu-O with increasing pH indicates the introduction of more asymmetry in the first sphere of adsorbed Eu(Ⅲ).At long contact time or high pH values,the Eu(Ⅲ) consists of ～2 Eu at REu-Eu ≈ 3.60 and ～ 1 Ti at REu-Ti ≈ 4.40 ,indicating the formation of inner-sphere surface complexation,surface precipitation or surface polymers.Surface adsorbed HA/FA on TNTs modifies the species of adsorbed Eu(Ⅲ) as well as the local atomic structures of adsorbed Eu(Ⅲ) on HA/FA-TNT hybrids.Adsorbed Eu(Ⅲ) on HA/FA-TNT hybrids forms both ligand-bridging ternary surface complexes(Eu-HA/FA-TNTs) as well as surface complexes in which Eu(Ⅲ) remains directly bound to TNT surface hydroxyl groups(i.e.,binary Eu-TNTs or Eu-bridging ternary surface complexes(HA/FA-Eu-TNTs)).The findings in this work are important to describe Eu(Ⅲ) interaction with nanomaterials at molecular level and will help to improve the understanding of Eu(Ⅲ) physicochemical behavior in the natural environment.
基金supported by the National Natural Science Foundation of China(91226113,J1210001)
文摘Humic substances(HS) substantially affect heavy metal(M) adsorption on mineral surfaces. However, quantitative descriptions of ternary systems involving M, HS and mineral surfaces remain unclear. This study examines adsorption in a model ternary system including Eu(III), fulvic acid(FA) and silica, and describes the adsorption of Eu(III) and FA by combining a double-layer model(DLM) and the Stockholm humic model(SHM). SHM explains the binding of H+ and Eu3+ to FA and the DLM for FA and Eu(III) adsorption on silica. Experimental results showed that the presence of FA promotes Eu(III) adsorption at acidic pH values, but decreases it at basic pH values, which indicates the formation of ternary surface complexes. Modeling calculations have shown that two ternary surface complexes are required to describe the experimental results in which Eu3+ acts as a bridge between the surface site and FA. The present study suggests that the discrete-site approach to HS is a promising method for interpreting the adsorption data for M, HS and mineral ternary systems.
