The sorption behavior and microscopic sequestration mechanisms of radionuclide 63Ni(II) on mordenite as a function of aging time,ionic strength,initial 63Ni(Ⅱ) concentrations,solid content and coexistent electrolyte ...The sorption behavior and microscopic sequestration mechanisms of radionuclide 63Ni(II) on mordenite as a function of aging time,ionic strength,initial 63Ni(Ⅱ) concentrations,solid content and coexistent electrolyte ions were investigated by the com-bination of batch and EXAFS techniques.Macroscopic experiment results show that the sorption of 63Ni(Ⅱ) is dependent on ionic strength at pH<7,and independent of ionic strength at pH>7.The sorption percentage of 63Ni(Ⅱ) on mordenite increases with increasing solid content,while the sorption capacity decreases as solid content increases.The presence of different elec-trolyte ions can enhance or inhibit the sorption of Ni(II) on mordenite in various degrees.EXAFS analysis results of the sam-ples under three different ionic strengths suggest that the retained 63Ni(Ⅱ) in these samples exists in an octahedral environment with six water ligands.In the initial period of rapid uptake,the sorption of 63Ni(Ⅱ) is dominated by the formation of in-ner-sphere surface complexes.As aging time increases,63Ni(Ⅱ) sequestration behavior tends to be mainly controlled by the formation of Ni phyllosilicate co-precipitates and/or Ni(OH)2(s) precipitates.Results for the second shell fit of the sample pre-pared at an initial 63Ni(Ⅱ) concentration of 100 mg/L indicate the possible formation of Ni polynuclear surface complexes.Both the macroscopic sorption data and the molecular level evidence of 63Ni(Ⅱ) surface speciation at the mordenite/water in-terfaces should be factored into better predictions of the mobility and bioavailability of 63Ni(Ⅱ) in environment mediums.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 (2011CB933700)the Knowledge Innovation Program of CAS and Special Foundation for High-level Waste Disposal (2007-840)
文摘The sorption behavior and microscopic sequestration mechanisms of radionuclide 63Ni(II) on mordenite as a function of aging time,ionic strength,initial 63Ni(Ⅱ) concentrations,solid content and coexistent electrolyte ions were investigated by the com-bination of batch and EXAFS techniques.Macroscopic experiment results show that the sorption of 63Ni(Ⅱ) is dependent on ionic strength at pH<7,and independent of ionic strength at pH>7.The sorption percentage of 63Ni(Ⅱ) on mordenite increases with increasing solid content,while the sorption capacity decreases as solid content increases.The presence of different elec-trolyte ions can enhance or inhibit the sorption of Ni(II) on mordenite in various degrees.EXAFS analysis results of the sam-ples under three different ionic strengths suggest that the retained 63Ni(Ⅱ) in these samples exists in an octahedral environment with six water ligands.In the initial period of rapid uptake,the sorption of 63Ni(Ⅱ) is dominated by the formation of in-ner-sphere surface complexes.As aging time increases,63Ni(Ⅱ) sequestration behavior tends to be mainly controlled by the formation of Ni phyllosilicate co-precipitates and/or Ni(OH)2(s) precipitates.Results for the second shell fit of the sample pre-pared at an initial 63Ni(Ⅱ) concentration of 100 mg/L indicate the possible formation of Ni polynuclear surface complexes.Both the macroscopic sorption data and the molecular level evidence of 63Ni(Ⅱ) surface speciation at the mordenite/water in-terfaces should be factored into better predictions of the mobility and bioavailability of 63Ni(Ⅱ) in environment mediums.
