小分子有机酸对秸秆生物炭/蒙脱土复合物吸附卡马西平的影响及阈值效应

The Influence of Small Molecule Organic Acids on the Adsorption of Carbamazepine by Straw Biochar/Montmorillonite Complex and the Threshold Effect

  • 摘要: 农作物秸秆生物炭作为一种绿色高效的污染修复材料,在去除土壤中药用活性化合物(PhACs)方面具有显著的环境效益和经济优势。其中,卡马西平(Carbamazepine,CBZ)作为PhACs中一种具持久性环境风险的污染物,是土壤中重要的待去除目标物质。然而,植物根系分泌和有机质降解产生的小分子有机酸(LMWOA)对秸秆生物炭吸附CBZ能力的影响仍认识不清。本文通过室内批实验和色谱法测试,探究玉米、小麦和水稻三种农作物秸秆生物炭添加到蒙脱土后对CBZ的吸附能力,以及柠檬酸与草酸两种LMWOA对上述吸附过程的影响作用。结果表明,随着CBZ浓度增加,蒙脱土对其吸附能力逐渐提升。O/C、H/C和(O+N)/C与吸附亲和系数KF之间的显著相关性表明,秸秆生物炭吸附CBZ是孔隙填充、疏水作用、π–π相互作用等物理和化学吸附机制共同作用的结果。其中,水稻生物炭由于表面芳香性和非极性更强,其对CBZ的最大吸附量达到115.6mg/g,显著高于玉米生物炭和小麦生物炭的13.1mg/g和19.5mg/g。尽管柠檬酸与草酸的加入造成CBZ在蒙脱土上的吸附系数(Kd)降低了99%,但其对秸秆生物炭的CBZ吸附能力几乎没有影响。LMWOA在蒙脱土-生物炭复合体系吸附CBZ的过程中表现出的“低浓度促进,高浓度抑制”阈值效应,说明了其会对矿物-生物炭界面相互作用产生影响。本研究结果说明秸秆生物炭添加至土壤中可显著提升对CBZ的吸附能力,表明其作为土壤修复剂具有良好的抵抗环境干扰能力和应用潜力。

     

    Abstract: Crop straw biochar, as a green and efficient pollution remediation material, demonstrates significant environmental benefits and economic advantages in removing pharmaceutical active compounds (PhACs) from soil. Carbamazepine (CBZ), a persistent environmental risk pollutant within PhACs, represents a crucial target substance for removal from soil. However, the impact of low molecular weight organic acids (LMWOAs) produced by plant root exudates and organic matter degradation on the CBZ adsorption capacity of straw biochar remains poorly understood. This study investigates the adsorption capacity of biochar derived from corn, wheat, and rice straws on CBZ in montmorillonite through laboratory batch experiments and chromatographic analysis, as well as the influence of two LMWOAs (citric acid and oxalic acid) on the adsorption process. The results indicate that the adsorption capacity of montmorillonite for CBZ progressively increases with higher CBZ concentrations. Significant correlations between O/C, H/C, and (O+N)/C ratios with the adsorption affinity coefficient KF suggest that CBZ adsorption by straw biochar results from the combined effects of physical and chemical adsorption mechanisms, including pore filling, hydrophobic interactions, and π–π interactions. Notably, rice straw biochar exhibits the highest maximum adsorption capacity for CBZ at 115.6mg/g, significantly surpassing corn straw biochar (13.1mg/g) and wheat straw biochar (19.5mg/g), attributed to its stronger surface aromaticity and non-polarity. Although the addition of citric acid and oxalic acid reduces the adsorption coefficient (Kd) of CBZ on montmorillonite by 99%, it has minimal impact on the CBZ adsorption capacity of straw biochar. The threshold effect of LMWOAs in the montmorillonite-biochar composite system, characterized by “low concentration promotion and high concentration inhibition” in CBZ adsorption, indicates their influence on mineral-biochar interface interactions. These findings demonstrate that the incorporation of straw biochar into soil significantly enhances CBZ adsorption capacity, suggesting its potential as a soil remediation agent with robust resistance to environmental interference and promising application prospects. The BRIEF REPORT is available for this paper at http://www.ykcs.ac.cn/en/article/doi/10.15898/j.ykcs.202505160124.

     

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