腐殖酸调控Fe(II)诱导水铁矿转化及其对镉固存的影响机制
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1.华南理工大学环境与能源学院;2.中国科学院广州地球化学研究所电子显微镜中心实验室

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国家自然科学基金项目(42025701,42307297)资助


Mechanism of Humic Acid Regulated Fe(II)-Induced Ferrihydrite Transformation and Its Impact on Cadmium Sequestration
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Affiliation:

1.School of Environment and Energy, South China University of Technology;2.Electron Microscopy Center, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences

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Supported by the National Natural Science Foundation of China (Nos. 42025701and 42307297)

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    摘要:

    铁氧化物在自然环境中的转化过程对重金属迁移具有重要影响,腐殖酸(HA)作为土壤和水体中的重要有机组分,可调控该过程。通过透射电镜(TEM)-能量色散谱(EDS)-电子能量损失谱(EELS)技术,系统探讨了Fe(II)诱导下水铁矿(Fh)向晶态铁氧化物(纤铁矿Lp、针铁矿Gt和磁铁矿Mt)的转化动力学,及其对镉(Cd)固存的影响。结果表明,在Fh-Cd体系中,6 h时Lp(48.08%)和Gt(43.49%)迅速形成,120 h后Lp持续转化为Gt,至168 h时少量Mt(4.82%)生成。在Fh-HA-Cd体系中,HA显著抑制转化速率,Lp和Gt形成较慢,168 h时矿物组成为Fh(2.63%)、Lp(42.79%)和Gt(54.6%),未检测到Mt。在转化过程中,固相HA浓度从4.94 mmolL-1降至4.49 mmolL-1,固相Cd浓度在6 h后迅速下降,随后趋于稳定,Fh-Cd体系固相Cd浓度较Fh-HA-Cd体系高约5%~10%。TEM高角环形暗场和EDS分析显示,初始状态下碳(C)和Cd与Fh高度相关,转化后Lp和Gt对Cd吸附能力仍较强,但对C的吸附显著减弱。EELS线扫进一步揭示,C主要固存于Fh表面及Lp的缺陷和孔隙中,含碳官能团(C-H、C=O、C-OH)在转化中逐渐脱附,而Cd通过吸附、结构取代及物理包裹等多种机制保留于新形成的铁氧化物中。上述结果表明,HA通过抑制铁氧化物转化和增强Cd吸附能力,显著影响Cd的地球化学行为,为理解铁氧化物-有机质-重金属相互作用机制提供了重要科学依据。

    Abstract:

    【Objective】Iron oxides play a pivotal role in the migration of heavy metals in natural environments, with humic acid (HA), a major organic component in soils and water bodies, potentially exerting significant regulatory effects on these processes. This study aims to systematically investigate the transformation kinetics of ferrihydrite (Fh) into crystalline iron oxides (lepidocrocite Lp, goethite Gt, and magnetite Mt) and its impact on cadmium (Cd) sequestration.【Method】Using transmission electron microscopy (TEM) coupled with energy-dispersive spectroscopy (EDS) and electron energy loss spectroscopy (EELS), this study conducted a controlled experiment involving Fh-Cd (control) and Fh-HA-Cd systems. Fe(II) was introduced as a catalyst to initiate the transformation, which was monitored over 168 h. The study examined the effects of HA (initial concentration 4.94 mmolL-1) and Cd (initial concentration 88.29–94.27 μmolL-1) on mineral phase evolution, Cd adsorption, and retention mechanisms.【Result】The results revealed that in the Fh-Cd system, Lp (48.08%) and Gt (43.49%) formed rapidly within 6 h, with Lp continuing to transform into Gt by 120 h, and a small amount of Mt (4.82%) emerging by 168 h. In contrast, in the Fh-HA-Cd system, HA significantly inhibited the transformation rate, resulting in slower formation of Lp and Gt, with a final mineral composition at 168 h of Fh (2.63%), Lp (42.79%), and Gt (54.6%), and no detectable Mt. During the transformation, the solid-phase HA concentration decreased from 4.94 mmolL-1 to 4.49 mmolL-1, and Cd concentration in the solid phase dropped sharply after 6 h before stabilizing, with the Fh-HA-Cd system exhibiting 5%–10% higher solid-phase Cd than the Fh-Cd system. TEM-high angle annular dark field and EDS analyses showed that C and Cd were initially closely associated with Fh; post-transformation, Lp and Gt retained strong Cd adsorption but exhibited significantly reduced C adsorption. EELS line scans further indicated that C was primarily retained on Fh surfaces and within defects/porosities of Lp, with carbon functional groups (C-H, C=O, C-OH) desorbing during transformation, while Cd was retained through multiple mechanisms including adsorption, structural substitution, and physical encapsulation in the newly formed iron oxides.【Conclusion】This study demonstrates that HA significantly influences Cd’s geochemical behavior by suppressing iron oxide transformation and enhancing Cd adsorption. These findings provide valuable scientific insights into the interaction mechanisms among iron oxides, organic matter, and heavy metals, offering a theoretical basis for understanding and managing Cd contamination in natural systems.

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梁斌,刘福,朱润良,邢介奇,张烨坤,肖智方,叶倩婷,王雯霞,石振清.腐殖酸调控Fe(II)诱导水铁矿转化及其对镉固存的影响机制[J].土壤学报,2026,63(1). DOI:10.11766/trxb202506230300 LIANG Bin, LIU Fu, ZHU Runliang, XING Jieqi, ZHANG Yekun, XIAO Zhifang, YE Qianting, WANG Wenxia, SHI Zhenqing. Mechanism of Humic Acid Regulated Fe(II)-Induced Ferrihydrite Transformation and Its Impact on Cadmium Sequestration[J]. Acta Pedologica Sinica,2026,63(1).

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  • 收稿日期:2025-06-23
  • 最后修改日期:2025-09-08
  • 录用日期:2025-09-24
  • 在线发布日期: 2025-09-28
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