淋洗剂施用顺序调控下重金属污染土壤修复效能与机理研究

Remediation performance and mechanisms of heavy metal-contaminated soil under the regulation of washing agent application sequence

  • 摘要: 为探究不同淋洗顺序修复重金属污染土壤的效果及机理,以云南某铅锌矿区镉(Cd)、铅(Pb)、锌(Zn)高浓度污染土壤为对象,将乙二胺四乙酸(EDTA)、氯化铁(FeCl3)、柠檬酸(CA)作为淋洗剂,通过单因素优化、循环淋洗、不同顺序淋洗及淋洗动力学实验,结合X射线衍射(XRD)和傅里叶变换红外光谱(FT-IR)对淋洗前后土壤微观结构进行表征。结果表明:EDTA、FeCl3和CA的最佳浓度分别为0.25 mol/L、0.30 mol/L、0.30 mol/L,最佳反应时间分别为120 min、120 min、180 min,最佳液固比分别为15∶1、20∶1、20∶1。循环6次淋洗结果显示,FeCl3对Cd、Zn和Pb的持久去除能力显著优于EDTA和CA,总去除率分别达87.35%、42.40%和66.87%;不同顺序淋洗中,FeCl3→EDTA的淋洗顺序对Cd和Pb表现出最佳的去除效果;淋洗后土壤主要矿物组成与官能团未发生显著改变。动力学拟合表明,Elovich和双常数方程能较好描述淋洗过程,其解吸机制以非均相扩散为主。研究表明,FeCl3在循环淋洗中更具应用潜力,且通过优化淋洗剂组合顺序可实现重金属的靶向强化去除,FeCl3→EDTA的淋洗顺序修复效果最佳,为矿区高浓度重金属污染土壤的化学淋洗修复提供了理论依据和技术参考。

     

    Abstract: To investigate the effectiveness and mechanisms of remediating heavy metal-contaminated soil under different washing sequences, we selected soil highly contaminated with Cd, Pb, and Zn from a lead–zinc mining area in Yunnan Province as the test soil. Ethylenediaminetetraacetic acid (EDTA), ferric chloride (FeCl3), and citric acid (CA) were employed as washing agents. The microstructure of the soil before and after washing was characterized through single-factor optimization, cyclic washing, washing sequential trials, and washing kinetics experiments, combined with X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FT-IR). The results showed that the optimal concentrations of EDTA, FeCl3, and CA were 0.25 mol/L, 0.30 mol/L, and 0.30 mol/L, with optimal reaction times of 120 min, 120 min, and 180 min, and optimal liquid-to-solid ratios of 15∶1, 20∶1, and 20∶1, respectively. After six washing cycles, FeCl3 exhibited markedly superior long-term removal capability for Cd, Zn, and Pb compared with EDTA and CA, achieving total removal rates of 87.35%, 42.40%, and 66.87%, respectively. Among various washing sequences, the FeCl3→EDTA sequence demonstrated the highest removal performance for Cd and Pb. The major mineral composition and functional groups of the soil showed no significant changes after washing. Kinetic fitting indicated that the Elovich and two-constant equations provided a good description of the washing process, with desorption primarily dominated by heterogeneous diffusion. Overall, this study demonstrates that FeCl3 holds greater potential for application in cyclic washing, and that optimizing the sequence of washing agents can achieve targeted and enhanced removal of heavy metals. The FeCl3→EDTA washing sequence yields the optimal remediation performance, providing a theoretical basis and technical reference for chemical washing remediation of high-concentration heavy metal-contaminated soils in mining areas.

     

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