Effects of Goethite/Birnessite on Antimony Speciation in Yellow Soil from an Antimony Mining Area under Simulated Natural Conditions
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摘要:
锑矿区及周边土壤锑污染严重，锑污染程度与其在土壤中的存在形态关系密切。铁锰氧化物是土壤黏土矿物中最活跃的成分，影响着锑在土壤中的形态转化。现有研究更多关注铁锰氧化物单一矿物对外源锑吸附的影响，而铁锰氧化物对实际土壤中锑形态转化的影响方面的基础研究有待加强。本文将土壤中常见的针铁矿(α-FeOOH)和水钠锰矿(δ-MnO2)以原位制备的方式，分别负载在贵州晴隆锑矿区的锑污染黄壤(原土)中，制得载铁土和载锰土，模拟土壤自然状况，淹水180天，探究了α-FeOOH和δ-MnO2介导下土壤锑形态的转化特征。结果表明，淹水改变了土壤氧化还原特性，影响铁锰氧化物的赋存形态，进而影响锑的形态分布，负载的α-FeOOH主要以无定形铁存在，负载的δ-MnO2以游离锰、无定形锰和络合锰三种形式存在。与原土相比，载铁土悬浮液锑和弱酸提取态锑含量分别降低88.3%～94.4%、21.1%～65.9%，可还原态锑和可氧化态锑含量分别增加49.0%～67.2%、74.3%～159%；载锰土中悬浮液锑、弱酸提取态锑和可还原态锑分别增加14.2%～59.5%、6.50%～32.6%、4.80%～23.3%，可氧化态锑降低16.2%～58.5%。即原土、载铁土和载锰土各形态铁、锰、锑在淹水30天变化明显或是变化趋势发生转折，负载α-FeOOH促进了土壤弱酸提取态锑向土壤可还原态锑和可氧化态锑转化，负载δ-MnO2促进了土壤可氧化态锑向土壤弱酸提取态锑和可还原态锑转化。该研究为锑污染土壤的风险评估和修复技术提供了关键科学依据，对土壤锑污染的控制需结合铁锰氧化物形态调控和氧化还原条件管理，以实现锑的长期稳定化。
Abstract:The antimony (Sb) mining area and its surrounding soil are severely polluted with antimony, and the degree of antimony pollution is closely related to its speciation in the soil. Iron and manganese oxides are the most active components of clay minerals in soil, affecting the transformation of antimony speciation in soil. Existing research focuses more on the effect of single iron and manganese oxides on the adsorption of exogenous antimony, while basic study on the effect of iron and manganese oxides on the transformation of antimony speciation in actual soil needs to be strengthened. This study described the in situ preparation of goethite (α-FeOOH) and birnessite (δ-MnO2) in soil, which were loaded onto antimony contaminated yellow soil (original soil) in the Qinglong antimony mining area, Guizhou Province to obtain Fe-loaded soil and Mn-loaded soil. Simulating the natural soil conditions, a 180-day flooding experiment of original soil, Fe-loaded soil and Mn-loaded soil was conducted. The transformation characteristics of soil antimony forms mediated by α-FeOOH and δ-MnO2 were explored. The results showed that flooding changed the redox characteristics of soil, affected the forms of iron and manganese oxides, and thus affected the distribution of antimony speciation. The loaded α-FeOOH mainly existed as amorphous iron, while the loaded δ-MnO2 existed in three forms: free manganese, amorphous manganese, and complex manganese. Compared with the original soil, the content of Sb in the suspension and weak acidic extracted antimony of Fe-loaded soil decreased by 88.3%−94.4% and 21.1%−65.9%, respectively; the content of reducible antimony and oxidizable antimony increased by 49.0%−67.2% and 74.3%−159%, respectively; Sb in the suspension, weak acidic extracted antimony, and reducible antimony in Mn-loaded soil increased by 14.2%−59.5%, 6.50%−32.6%, and 4.80%−23.3%, respectively, while oxidizable antimony decreased by 16.2%−58.5%. The various speciation of iron, manganese, and antimony in the original soil, Fe-loaded soil and Mn-loaded soil showed significant changes or a turning point in the trend after 30 days of flooding. Loading α-FeOOH promoted the transformation of weak acidic extracted antimony to reducible and oxidizable antimony in the soil, while loading δ-MnO2 promoted the transformation of oxidizable antimony to weak acidic extracted antimony and reducible antimony in the soil. This study provides a key scientific basis for the risk assessment and remediation technology of antimony contaminated soil. In the future, the control of soil antimony pollution needs to be combined with the regulation of iron and manganese oxide forms and the management of redox conditions to achieve long-term stabilization of antimony. The BRIEF REPORT is available for this paper at
http://www.ykcs.ac.cn/en/article/doi/10.15898/j.ykcs.202502280032 .-
Key words:
- α-FeOOH /
- δ-MnO2 /
- soil /
- antimony /
- speciation transformation /
- atomic absorption spectroscopy
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