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<p>Clogging of zero-valent iron (ZVI) is among the most prominent technical bottlenecks limiting its application in long-term groundwater remediation. In this study, three ZVI species with different oxygenated anion modifications on the surface—micron ZVI (mZVI), oxalated mZVI (OX-mZVI), and phosphorylated mZVI (P-mZVI)—were selected to conduct a comparative study on the clogging problem during remediation of nitrobenzene-contaminated groundwater. The clogging degree (Φ<sub>C</sub>) was innovatively employed to quantify ZVI clogging, and the clogging mechanisms of influencing factors were uncovered by analyzing changes in Φ<sub>C</sub>, reactivity, volume expansion, iron valence state, and iron corrosion product (FeCP) species. Results revealed that the clogging resistance of ZVI decreased in the following order: P-mZVI &gt; OX-mZVI &gt; mZVI. The reduction process of nitrobenzene controlled the increase of Φ<sub>C</sub>, and the reduction of NO<sub>3</sub><sup>−</sup>—a groundwater background ion—served as an indicator for clogging stage changes. Surface chemistry analysis revealed that the increase of Φ<sub>C</sub> originated from the volume expansion effect of FeCPs. Iron corrosion increased the Fe(III) content, producing Fe<sub>3</sub>O<sub>4</sub> and FeOOH, which roughened the ZVI surfaces and formed dense agglomerates via crystal expansion, causing chemical clogging by occupying pore space. Overall, enhancing the electron selectivity and surface hydrophobicity of ZVI using surface modification methods can enhance its anti-clogging performance.</p>

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Insights on mitigation of chemical clogging of zero-valent iron for nitrobenzene reduction: the role of oxygenated anion modification

  • 期刊论文

  • 发表日期：

    2025年6月15日

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  • Yuyang Bai,
  • Zhichao Yun,
  • Fu Xia,
  • Sheng Deng,
  • Qiyuan Liu,
  • Shuxuan Wu,
  • Xu Han,
  • Yu Yang,
  • Yonghai Jiang

摘要

Clogging of zero-valent iron (ZVI) is among the most prominent technical bottlenecks limiting its application in long-term groundwater remediation. In this study, three ZVI species with different oxygenated anion modifications on the surface—micron ZVI (mZVI), oxalated mZVI (OX-mZVI), and phosphorylated mZVI (P-mZVI)—were selected to conduct a comparative study on the clogging problem during remediation of nitrobenzene-contaminated groundwater. The clogging degree (ΦC) was innovatively employed to quantify ZVI clogging, and the clogging mechanisms of influencing factors were uncovered by analyzing changes in ΦC, reactivity, volume expansion, iron valence state, and iron corrosion product (FeCP) species. Results revealed that the clogging resistance of ZVI decreased in the following order: P-mZVI > OX-mZVI > mZVI. The reduction process of nitrobenzene controlled the increase of ΦC, and the reduction of NO3−—a groundwater background ion—served as an indicator for clogging stage changes. Surface chemistry analysis revealed that the increase of ΦC originated from the volume expansion effect of FeCPs. Iron corrosion increased the Fe(III) content, producing Fe3O4 and FeOOH, which roughened the ZVI surfaces and formed dense agglomerates via crystal expansion, causing chemical clogging by occupying pore space. Overall, enhancing the electron selectivity and surface hydrophobicity of ZVI using surface modification methods can enhance its anti-clogging performance.