腐植酸与水钠锰矿交互作用对锑矿区黄壤中锑形态的影响

Effects of Interaction between Humic Acid and Birnessite on Antimony Speciation in Yellow Soil from Antimony Mining Areas

  • 摘要: 矿区土壤锑(Sb)污染严重,其环境风险主要取决于锑化学形态。锰氧化物(如水钠锰矿,δ-MnO2)和腐植酸是土壤中调控锑形态转化的关键活性组分。目前研究多聚焦于两者对锑的单一吸附行为,但对其交互作用的研究较少,尤其是针对真实土壤环境。本文采用原位制备的方式,在矿区锑重度污染黄壤上负载0.1%的δ-MnO2,加入土壤质量1.0%、2.0%、3.0%和5.0%的腐植酸,淹水40天,分析土壤中锰、锑各形态含量的变化,探究腐植酸与δ-MnO2的交互作用对土壤各形态锑转化的影响机制。结果表明,随着腐植酸添加量的增加,原土组中的悬浮液锑和土壤弱酸提取态锑含量分别下降20.7倍和75.8%,土壤可还原态锑、可氧化态锑和残渣态锑含量分别增长75.4%、41.0%和4.6%;载锰土组中的悬浮液锑和弱酸提取态锑含量分别下降 41.2倍和84.6%,土壤可还原态锑、可氧化态锑和残渣态锑含量分别增长83.2%、2.9倍、7.9%。相较于原土,载锰土中弱酸提取态锑、可还原态锑含量分别增加19.4%~36.7%、41.3%~77.6%,当腐植酸含量>3.0%,可氧化态锑增长26.5%~38.2%。腐植酸和δ-MnO2协同作用将土壤中高活性的悬浮液锑和弱酸提取态锑转化为更稳定的可还原态、可氧化态和残渣态锑,从而降低了锑迁移性,这种作用与腐植酸添加量关系密切。研究结果为锰氧化物-腐植酸协同修复锑污染土壤提供了关键的理论支撑和应用路径。

     

    Abstract: Antimony (Sb) contamination in mining area soils is severe, and its environmental risk mainly depends on chemical speciation of Sb. Mn oxides and humic acids are key active components regulating Sb speciation in soil. At present, most of the research focuses on the single adsorption behavior toward Sb, but the interaction between them is less, especially for real soil environment. Using an in situ preparation method, 0.1% birnessite (δ-MnO2) was loaded on the Sb-heavily contaminated yellow soil in the mining area. Humic acid with 1.0%, 2.0%, 3.0%, and 5.0% of the soil mass was added. After 40 days of flooding, the changes of various forms of Mn and Sb in the soil were analyzed, and the influence mechanism of the interaction between humic acid and δ-MnO2 on the transformation of various forms of Sb in the soil was explored. The results indicate that with increase of humic acid addition, the content of suspended Sb and weakly acid-extractable Sb in the original soil group decrease by 20.7 time and 75.8%, respectively. Meanwhile, the content of reducible Sb, oxidizable Sb, and residual Sb increase by 75.4%, 41.0%, and 4.6%, respectively. In the Mn-loaded soil group, suspended Sb and weakly acid-extractable Sb decrease by 41.2 times and 84.6 times, respectively, while reducible Sb, oxidizable Sb, and residue Sb increase by 83.2%, 2.9 times, and 7.9 times, respectively. Compared with the original soil, the contents of weakly acid-extractable Sb and reducible Sb in Mn-loaded soil increase by 19.4%–36.7% and 41.3%-–77.6%, respectively. When humic acid content is greater than 3.0%, the content of oxidizable Sb increases by 26.5%–38.2%. Humic acid and δ-MnO2 can synergistically convert highly mobile suspended Sb and weakly acid-extractable Sb in soil into more stable reducible, oxidizable, and residual forms, thereby reducing Sb migration. These findings provide a critical theoretical support and practical pathway for the synergistic remediation of Sb-contaminated soils using Mn oxides and humic acid.

     

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