电场影响下耕地土壤镉吸附动力学特征与机制

Characteristics and Mechanisms of Cadmium Adsorption Kinetics in Arable Soil Under the Influence of Electric Field

  • 摘要:
    目的 基于土壤电化学理论,探究不同类型耕地土壤对重金属镉(Cd)的吸附动力学特征。
    方法 以典型恒电荷土壤(黑土、黄棕壤、灌淤土)和可变电荷土壤(赤红壤、红壤)的耕地表层土作为研究对象,采用恒流混合置换法开展离子吸附动力学试验。利用考虑电场作用的吸附动力学模型对吸附试验数据进行拟合,获得Cd2 + 的吸附反应级数、平衡吸附量等动力学参数,计算离子-土壤表面相互作用能和扩散活化能。
    结果 除最低离子浓度(2.67 × 10−2 mmol L−1)下,Cd2 + 在黑土表面呈现零级和一级动力学吸附特征,其余处理Cd2 + 在5种土壤表面均呈现一级动力学吸附特征。5种土壤表面Cd2 + 平衡吸附量遵循黑土 > 黄棕壤 > 灌淤土 > 赤红壤 > 红壤的顺序,离子-土壤表面相互作用能的变化趋势大致遵循相同顺序,而扩散活化能的变化则呈现相反顺序。
    结论 Cd2 + 在5种耕地土壤表面的吸附动力学特征存在差异。Cd2 + 在恒电荷土壤中的吸附行为受黏粒、土壤有机碳和碳酸钙含量的共同影响,而pH值则主导可变电荷土壤对Cd2 + 的吸附行为。进一步研究发现,恒/可变电荷土壤的表面电荷数量和电场强度是影响其吸附Cd2 +的重要因素。随着土壤表面电荷数量和电场强度的提升,Cd2 + 与土壤表面之间相互作用增强,需要克服的扩散活化能势垒降低,导致Cd2 + 吸附量增加。本研究从电化学视角揭示了Cd2 + 在带电土壤表面的吸附机制。

     

    Abstract:
    Objective This study investigated the adsorption kinetic characteristics of heavy metal cadmium (Cd) adsorption by soils from different types of cultivated land based on soil electrochemical theory.
    Method Typical arable topsoil samples from permanently charged soils (Black soil, Yellow brown soil, Anthropogenic alluvial soil) and variably charged soils (Latosolic red soil, Red soil) were collected as the research object. Ion adsorption kinetic experiments were conducted using miscible displacement technology. The adsorption experimental data were fitted using an adsorption kinetic model that takes into account the role of the electric field, to characterize the number of adsorption reaction levels, the equilibrium adsorption amount and other kinetic parameters of Cd2 + , and to calculate the ion- soil surface interaction energy and diffusion activation energy.
    Result Except for the lowest ion concentration (2.67 × 10−2 mmol L−1), Cd2 + showed zero-order and first-order adsorption kinetic on the black soil surface, the rest of the treatments showed first-order adsorption kinetic of Cd2 + on the surfaces of the five soils. The equilibrium adsorption of Cd2 + on the surfaces of the five soils followed the order of Black soil > Yellow brown soil > Anthropogenic alluvial soil > Latosolic red soil > Red soil, and the trends of the ion-soil surface interaction energies roughly followed the same order, while the changes in the diffusion activation energies showed the opposite order. The adsorption kinetics of Cd2+ on the surfaces of five different agricultural soils exhibit differences. The adsorption behavior of Cd2 + in constant charge soils was jointly influenced by clay particles, organic carbon and calcium carbonate content, while pH dominates the adsorption behaviour of Cd2 + by the variable charge soils. The further findings showed that the surface charge number and the surface electric field intensity of the permanently/variably charged soils were important factors influencing their adsorption of Cd2 + . As the surface charge number and the surface electric field intensity of the soils were elevated, the interaction between Cd2 + and the soil surface was intensified and the required diffusion activation energy was lowered, leading to an increase in Cd2 + adsorption.
    Conclusion The results elucidate the adsorption mechanism of Cd2+ on charged soil surfaces from an electrochemical perspective, and may provide new insights into the modelling and prediction of the environmental behaviour of heavy metals in agricultural soils.

     

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