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生态学杂志 ›› 2024, Vol. 43 ›› Issue (9): 2834-2841.doi: 10.13292/j.1000-4890.202409.028

• 污染与环境生态 • 上一篇    下一篇

铁锰氧化物和黏土矿物对正构烃非生物自然衰减过程的影响与作用机制

张燕子1,2,刘长风1,闫秀秀2,3,安婧2*   

  1. 1沈阳化工大学环境与安全工程学院, 沈阳 110142; 2中国科学院污染生态与环境工程重点实验室, 中国科学院沈阳应用生态研究所, 沈阳 110016; 3中国科学院大学, 北京 100049)

  • 出版日期:2024-09-10 发布日期:2024-09-14

Effect and mechanism of Fe-Mn oxides and clay minerals on abiotic natural attenuation of normal alkanes.

ZHANG Yanzi1,2, LIU Changfeng1, YAN Xiuxiu2,3, AN Jing2*   

  1. (1College of Environmental and Safety Engineering, Shenyang University of Chemical Technology, Shenyang 110142, China; 2Key Laboratory of Pollution Ecology and Environmental Engineering, Institute of Applied Ecology, Chinese Academy of Sciences, Shenyang 110016, China; 3University of Chinese Academy of Sciences, Beijing 100049, China).

  • Online:2024-09-10 Published:2024-09-14

摘要: 土壤组分中铁锰氧化物和黏土矿物(FeMn-Clay minerals, FM-C)在有机污染物的非生物转化中发挥着重要的作用,而有关黑暗环境下FM-C对正构烃的非生物自然衰减过程和作用机制鲜有报道。本研究以正构烃中长链C16~C31为对象,探讨无机矿物磁铁矿(Fe3O4)、赤铁矿(Fe2O3)、针铁矿(FeO(OH))、软锰矿(MnO2)、蒙脱石和高岭石在黑暗环境下对正构烃的非生物自然衰减的影响和作用机制。通过人工合成土壤,剔除自然土壤中所含的复杂元素,设置FM-C的浓度梯度(1%、2%、3%)来考察FM-C含量对正构烃降解的影响。结果表明,在黏土矿物表面上的铁锰氧化物会加速正构烃的降解和转化,且降解率随着FM-C的浓度增加而增加。采用X射线光电子能谱技术对反应前后黏土矿物上铁锰离子进行了半定量研究,结果显示,Fe(Ⅱ)和Mn(Ⅲ)的作用效果尤为明显,这是因为Fe(Ⅱ)和Mn(Ⅲ)可以直接与矿物上所吸附的氧气反应生成超氧自由基(O2-·)。通过电子顺磁共振技术检测发现,在正构烃转化降解过程中O2-·反应前后具有明显的变化,并且在正构烃的降解转化过程中起到了促进作用,从而提出了FM-C对正构烃降解转化的反应机理。本研究对在黑暗条件下土壤中无机矿物对正构烃类有机污染物的非生物自然衰减作用提供了有价值的见解。


关键词: 铁锰氧化物, 黏土矿物, 超氧自由基, 正构烃, 降解

Abstract:

Soil constitutions, especially iron oxides, manganese oxides and clay minerals (FeMn-Clay minerals, FM-C), exert a distinguished role in the transformation of organic contaminants. However, the contribution of FM-C to abiotic natural attenuation of normal alkanes in the dark has long been overlooked. In this study, a sterile experiment was conducted to examine the effects of different contents (1%, 2%, 3%) of iron oxides (Fe3O4, Fe2O3 and FeO(OH)), manganese oxides (MnO2) and clay minerals (kaolinite and montmorillonite) on the degradation of normal alkanes (long-chain C16-C31). The results showed that 3% FM-C possessed the highest transformation rate for normal alkanes, with a transformation rate up to 52.79% in 63 h. X-ray photoelectron spectroscopy (XPS) characterization suggested that Fe(Ⅱ) had the strongest effect, which was conducive to directly convert O2 into superoxide radical (O2-·). FM-C had the higher oxygen vacancy concentration, providing sufficient adsorbed oxygen that was stimulative for transformation and degradation of normal alkanes. The O2-· signal before and after the reaction was detected by electron paramagnetic resonance (EPR). The results confirmed that the transformation of normal alkanes was accompanied by O2-·. FTIR characterizations showed that the abiotic natural attenuation of normal alkanes was accompanied by forming new functional groups (C-OH). Consequently, the promoting effects of FM-C on abiotic degradation of normal alkanes and the possible pathways were concluded. Our results provided valuable insights into the abiotic natural attenuation of normal alkanes by inorganic minerals in soils under dark conditions.


Key words: Fe-Mn oxide, clay mineral, superoxide radical, normal alkane, degradation