Department of Agricultural Chemistry, National Taiwan University, No 1, Sec 4, Roosevelt Road, Taipei 106, Taiwan.
J Environ Radioact. 2010 Jun;101(6):472-81. doi: 10.1016/j.jenvrad.2008.10.013. Epub 2008 Nov 26.
The dynamics of Cs and Sr sorption by soils, especially in the subtropics and tropics, as influenced by soil components are not fully understood. The rates and capacities of Cs and Sr sorption by selected subtropical and tropical soils in Taiwan were investigated to facilitate our understanding of the transformation and dynamics of Cs and Sr in soils developed under highly weathering intensity. The Langmuir isotherms and kinetic rates of Cs and Sr sorption on the Ap1 and Bt1 horizons of the Long-Tan (Lt) and the A and Bt1 horizons of the Kuan-Shan (Kt), Mao-Lin (Tml) and Chi-Lo (Cl) soils were selected for this study. Air-dried soil (<2mm) samples were reacted with of 7.5 x 10(-5) to 1.88 x 10(-3)M of CsCl (pH 4.0) or 1.14 x 10(-4) to 2.85 x 10(-3)M of SrCl(2) (pH 4.0) solutions at 25 degrees C. The sorption maximum capacity (q(m)) of Cs by the Ap1 and Bt1 horizons of the Lt soil (62.24 and 70.70 mmol Cs kg(-1) soil) were significantly (p<0.05) higher than those by the A and Bt1 horizons of the Kt and Cl soils (26.46 and 27.49 mmol Cs kg(-1) soil in Kt soil and 34.83 and 29.96 mmol Cs kg(-1) soil in Cl soil, respectively), however, the sorption maximum capacity values of the Lt and Tml soils did not show significant differences. The amounts of pyrophosphate extractable Fe (Fe(p)) were correlated significantly with the Cs and Sr sorption capacities (for Cs sorption, r(2)=0.97, p<1.0 x 10(-4); for Sr sorption, r(2)=0.82, p<2.0 x 10(-3)). The partition coefficient of radiocesium sorbed on soil showed the following order: Cl soil>>Kt soil>Tml soil>Lt soil. It was due to clay minerals. The second-order kinetic model was applied to the Cs and Sr sorption data. The rate constant of Cs or Sr sorption on the four soils was substantiality increased with increasing temperature. This is attributable to the availability of more energy for bond breaking and bond formation brought about by the higher temperatures. The rate constant of Cs sorption at 308 K was 1.39-2.09 times higher than that at 278K in the four soils. The activation energy of Cs and Sr sorbed by the four soils ranged from 7.2 to 16.7 kJ mol(-1) and from 15.2 to 22.4 kJ mol(-1), respectively. Therefore, the limiting step of the Cs(+) or Sr(2+) sorption on the soils was diffusion-controlled processes. The reactive components, which are significantly correlated with the Langmuir sorption maxima of Cs and Sr by these soils, substantially influenced their kinetic rates of Cs and Sr sorption. The data indicate that among components of the subtropical and tropical soils studied, short-range ordered sesquioxides especially Al- and Fe-oxides complexed with organics play important roles in influencing their capacity and dynamics of Cs and Sr sorption.
土壤中 Cs 和 Sr 的吸附动力学,特别是在亚热带和热带地区,受土壤成分的影响还不完全清楚。本研究旨在了解高度风化强度下发育的土壤中 Cs 和 Sr 的转化和动态,因此调查了台湾地区选定的亚热带和热带土壤对 Cs 和 Sr 的吸附速率和容量。选择龙潭(Lt)的 Ap1 和 Bt1 层以及关山大埔(Kt)、毛林(Tml)和治洛(Cl)土壤的 A 和 Bt1 层的 Langmuir 等温线和 Cs 和 Sr 吸附动力学速率进行了此项研究。将风干土壤(<2mm)样品与 7.5 x 10(-5) 至 1.88 x 10(-3)M 的 CsCl(pH 4.0)或 1.14 x 10(-4) 至 2.85 x 10(-3)M 的 SrCl(2)(pH 4.0)溶液在 25 摄氏度下反应。Lt 土壤的 Ap1 和 Bt1 层对 Cs 的吸附最大容量(q(m))(62.24 和 70.70 mmol Cs kg(-1)土壤)明显(p<0.05)高于 Kt 和 Cl 土壤的 A 和 Bt1 层(Kt 土壤中 26.46 和 27.49 mmol Cs kg(-1)土壤,Cl 土壤中 34.83 和 29.96 mmol Cs kg(-1)土壤),然而,Lt 和 Tml 土壤的吸附最大容量值没有显示出显著差异。焦磷酸盐可提取的 Fe(Fe(p))的量与 Cs 和 Sr 的吸附容量呈显著相关(对于 Cs 吸附,r(2)=0.97,p<1.0 x 10(-4);对于 Sr 吸附,r(2)=0.82,p<2.0 x 10(-3))。放射性铯在土壤上的分配系数的顺序为:Cl 土壤>>Kt 土壤>Tml 土壤>Lt 土壤。这是由于粘土矿物。Cs 和 Sr 吸附数据应用了二级动力学模型。四种土壤中 Cs 或 Sr 吸附的速率常数随着温度的升高而显著增加。这归因于较高温度下键断裂和键形成所需的更多能量。四种土壤中 308 K 时 Cs 吸附的速率常数比 278 K 时高 1.39-2.09 倍。Cs 和 Sr 被四种土壤吸附的活化能范围分别为 7.2 至 16.7 kJ mol(-1)和 15.2 至 22.4 kJ mol(-1)。因此,Cs(+)或 Sr(2+)在土壤上的吸附的限制步骤是扩散控制过程。与这些土壤对 Cs 和 Sr 的 Langmuir 吸附最大值显著相关的反应性成分极大地影响了它们对 Cs 和 Sr 的吸附动力学速率。数据表明,在所研究的亚热带和热带土壤的成分中,短程有序的三氧化物,特别是与有机物结合的 Al 和 Fe 氧化物,在影响它们的 Cs 和 Sr 吸附能力和动力学方面发挥着重要作用。