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硅基磁性生物炭的制备及其对镉(Ⅱ)和砷(Ⅲ)共污染水体的修复机制

[Preparation of Silicon-based Magnetic Biochar and Its Remediation Mechanism for Cd(Ⅱ) and As(Ⅲ) Co-contaminated Water].

作者信息

Tian Xin, Sun Qi, Chen Yao, Wang Jia-Hao, Ye Zheng-Qian, Zhao Ke-Li, Wu Ji-Zi

机构信息

College of Environmental and Resource Sciences, Zhejiang A&F University, Lin'an 311300, China.

Key Laboratory of Soil Contamination Bioremediation of Zhejiang Province, Zhejiang A&F University, Lin'an 311300, China.

出版信息

Huan Jing Ke Xue. 2025 Jan 8;46(1):282-295. doi: 10.13227/j.hjkx.202311141.

DOI:10.13227/j.hjkx.202311141
PMID:39721635
Abstract

Cadmium (Cd) and arsenic (As) often coexist in water and agricultural soils around mining areas, and it is difficult to remove them at the same time due to their opposite chemical behaviors. Therefore, this study employed a co-precipitation-pyrolysis method to synthesize silica-based magnetic biochar (SMB) materials for the remediation of water contaminated with both Cd and As. The optimization of preparation conditions involved introducing three different types of silicates (NaSiO, CaSiO,and SiO) into the biomass-magnetite mixture, followed by pyrolysis at various temperatures (300℃, 500℃, and 700℃), and the optimal preparation conditions were determined based on the composite batch experiments. Finally, batch experiments in both single-element and composite systems were used to systematically investigate the impact of initial pH, adsorption time, and initial concentration on the adsorption behavior of SMB for Cd(Ⅱ) and As(Ⅲ). The adsorption mechanism was elucidated by combining it with characterization analyses, such as SEM, FT-IR, and XRD. The composite adsorption test determined that the material obtained from a pyrolyzing biomass-magnetite mixture containing 5% CaSiO at 700℃ exhibited the most effective adsorption, with removal rates reaching 92.04% for Cd(Ⅱ) and 60.59% for As(Ⅲ) in Cd(Ⅱ) and As(Ⅲ) solutions with initial concentrations of 30 and 10 mg·L. Characterization including SEM, FT-IR, XRD, and BET showed that the material had a significant surface area, rich functional groups, and magnetic properties. In the single-element batch experiment, the optimal adsorption pH for Cd(Ⅱ) and As(Ⅲ) was 6, with equilibrium reached at 1 h and 8 h, respectively. The quasi-secondary kinetic model effectively described the adsorption process of Cd(Ⅱ) and As(Ⅲ) by SMB. In the composite system, the optimum adsorption pH was 7. The Freundlich model better fitted the isothermal adsorption processes of Cd(II) and As(III) by the materials. The results of the batch experiments in the composite system revealed that both synergistic and antagonistic effects existed between Cd(Ⅱ) and As(Ⅲ). Synergistic effects were manifested through the formation of A-type and B-type ternary surface complexes during the adsorption of As(Ⅲ) and Cd(Ⅱ) by SMB. The formation of A-type ternary surface complexes significantly enhanced the material's adsorption capacity for As(Ⅲ). However, in the coexistence system, the synergistic effect was primarily controlled by electrostatic interaction, co-precipitation, and the formation of B-type ternary surface complexes due to the preference for adsorbing As(Ⅲ). Antagonistic effects resulted from the competition between the two heavy metal elements for binding sites with hydroxyl groups. In summary, the synthesized SMB material demonstrated effective adsorption of both Cd and As in water, presenting a promising approach for the efficient remediation of water bodies co-contaminated with Cd(Ⅱ) and As(Ⅲ).

摘要

镉(Cd)和砷(As)在矿区周边的水体和农业土壤中常常共存,由于它们相反的化学行为,很难同时将它们去除。因此,本研究采用共沉淀-热解法合成了基于二氧化硅的磁性生物炭(SMB)材料,用于修复同时受Cd和As污染的水体。制备条件的优化包括将三种不同类型的硅酸盐(NaSiO、CaSiO和SiO)引入生物质-磁铁矿混合物中,然后在不同温度(300℃、500℃和700℃)下进行热解,并基于复合批次实验确定了最佳制备条件。最后,通过单元素和复合体系的批次实验,系统研究了初始pH、吸附时间和初始浓度对SMB对Cd(Ⅱ)和As(Ⅲ)吸附行为的影响。通过结合扫描电子显微镜(SEM)、傅里叶变换红外光谱(FT-IR)和X射线衍射(XRD)等表征分析来阐明吸附机制。复合吸附试验确定,在700℃下热解含5%CaSiO的生物质-磁铁矿混合物得到的材料表现出最有效的吸附效果,在初始浓度分别为30和10mg·L的Cd(Ⅱ)和As(Ⅲ)溶液中,Cd(Ⅱ)的去除率达到92.04%,As(Ⅲ)的去除率达到60.59%。包括SEM、FT-IR、XRD和比表面积分析(BET)在内的表征表明,该材料具有较大的表面积、丰富的官能团和磁性。在单元素批次实验中,Cd(Ⅱ)和As(Ⅲ)的最佳吸附pH均为6,分别在1h和8h达到吸附平衡。准二级动力学模型有效地描述了SMB对Cd(Ⅱ)和As(Ⅲ)的吸附过程。在复合体系中,最佳吸附pH为7。Freundlich模型更适合描述材料对Cd(II)和As(III)的等温吸附过程。复合体系的批次实验结果表明,Cd(Ⅱ)和As(Ⅲ)之间既存在协同效应也存在拮抗效应。协同效应通过SMB吸附As(Ⅲ)和Cd(Ⅱ)过程中形成A型和B型三元表面络合物得以体现。A型三元表面络合物的形成显著提高了材料对As(Ⅲ)的吸附能力。然而,在共存体系中,协同效应主要受静电相互作用、共沉淀以及由于对As(Ⅲ)吸附的偏好而形成的B型三元表面络合物的控制。拮抗效应是由于两种重金属元素对与羟基结合位点的竞争所致。综上所述,合成的SMB材料对水中的Cd和As均表现出有效的吸附作用,为高效修复同时受Cd(Ⅱ)和As(Ⅲ)污染的水体提供了一种有前景的方法。

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