College of Resources and Environment, Southwest University, The Key Laboratory of Eco-environments in Three Gorges Reservoir Region, Ministry of Education, Chongqing 400715, China; Chongqing Key Laboratory of Agricultural Resources and Environment, Chongqing 400716, China.
Chemosphere. 2014 Mar;99:41-8. doi: 10.1016/j.chemosphere.2013.09.030. Epub 2013 Nov 26.
Batch experiments and sequential extraction analysis were employed to investigate the effects of soil organic matter and CaCO3 on the adsorption and desorption of cadmium (Cd(2+)) onto and from two purple paddy soils, an acidic purple paddy soil (APPS) and a calcareous purple paddy soil (CPPS). The Cd(2+) adsorption isotherms on both soils could be well-described by the Langmuir and Freundlich equations. CPPS had a higher capacity and a stronger affinity for Cd(2+) adsorption compared with APPS. The adsorption process of Cd(2+) on APPS was dominated by electrostatic attractions, whereas the adsorption mechanism varied depending on the Cd(2+) concentrations in equilibrium solutions on CPPS. At low equilibrium concentrations, the adsorption process was primarily specific adsorption, but nonspecific adsorption dominated at high equilibrium concentrations. Removal of organic matter decreased the amount of Cd(2+) adsorption on both of the soils, slightly affected the Cd(2+) desorption rate and exchangeable Cd (EXC-Cd) in APPS and increased the desorption rate and EXC-Cd in CPPS, suggesting that the effect of organic matter on Cd(2+) adsorption-desorption depends on the soils. CPPS and APPS containing CaCO3 exhibited higher adsorption amounts but lower desorption rates and lower proportions of EXC-Cd than those of their corresponding soils without CaCO3, demonstrating that CaCO3 played an important role in Cd(2+) specific adsorption on soil. The changes in the thermodynamic parameters, including free energy (ΔG(0)), enthalpy (ΔH(0)) and entropy (ΔS(0)), as evaluated by the Van't Hoff equations, indicated that the adsorption was a spontaneous and endothermic process with the primary interaction forces of dipole interactions and hydrogen bonds on APPS, whereas both physical and chemical interactions dominated the adsorption on CPPS.
采用批量实验和连续提取分析的方法,研究了土壤有机质和碳酸钙对两种紫色水稻土(酸性紫色水稻土(APPS)和钙质紫色水稻土(CPPS))吸附和解吸镉(Cd(2+))的影响。两种土壤的 Cd(2+)吸附等温线均可用 Langmuir 和 Freundlich 方程很好地描述。CPPS 对 Cd(2+)的吸附容量和亲和力均高于 APPS。APPS 上 Cd(2+)的吸附过程主要受静电引力的控制,而 CPPS 上的吸附机制则取决于平衡溶液中 Cd(2+)的浓度。在低平衡浓度下,吸附过程主要是特异性吸附,但在高平衡浓度下,非特异性吸附占主导地位。去除有机质会减少 Cd(2+)在两种土壤上的吸附量,对 APPS 中 Cd(2+)的解吸速率和可交换态 Cd(EXC-Cd)影响较小,而增加 CPPS 中 Cd(2+)的解吸速率和 EXC-Cd,这表明有机质对 Cd(2+)吸附-解吸的影响取决于土壤。含碳酸钙的 CPPS 和 APPS 表现出更高的吸附量,但解吸速率和可交换态 Cd(EXC-Cd)的比例低于不含碳酸钙的对应土壤,这表明碳酸钙在土壤中对 Cd(2+)的特异性吸附中起着重要作用。通过 Van't Hoff 方程评估的热力学参数(包括自由能(ΔG(0))、焓(ΔH(0))和熵(ΔS(0)))的变化表明,吸附是一个自发的吸热过程,在 APPS 上主要的相互作用力是偶极相互作用和氢键,而 CPPS 上则主要是物理和化学相互作用。