铁还原颗粒对地下水中氯代乙烷的降解动力学差异及机制

Difference and mechanism of degradation kinetics of chlorinated ethane in groundwater by iron reduction particles

  • 摘要: 以零价铁(ZVI)为代表的铁还原颗粒广泛应用于氯代烃污染地下水的修复治理,然而其对难降解饱和氯代烃的反应活性及其中主导影响因素仍缺乏系统研究和深入探讨。采集华北某废弃有机溶剂厂高浓度氯代乙烷污染地下水,评估了6种铁还原颗粒〔4种粒径(100、200、400、800目)的微米尺度零价铁(mZVI)、纳米尺度零价铁(nZVI)和黄铁矿〕对实际污染地下水中1,1,2-三氯乙烷(1,1,2-TCA)的降解动力学差异,并结合冗余和相关性分析揭示影响铁还原颗粒反应活性的因素和规律。结果表明:nZVI反应组中,1,1,2-TCA的表观速率常数(kobs)和质量归一化速率常数(kM)最高,分别达到0.012 5 d−1和0.008 L/(g·d),其次是mZVI,黄铁矿还原作用最弱。铁还原颗粒添加量的增加虽可提升污染物降解率,但却导致单位质量的反应速率降低。表面归一化速率常数(kSA)方面mZVI更具优势,在相同添加量条件下,200目mZVI的kSA为nZVI的22倍。冗余分析表明,S、O、Cl、C等杂质含量及颗粒添加量制约了kobskM,而O、C、S含量及颗粒比表面积与kSA相关性最大,且相关性分析表明O、C含量及颗粒比表面积与kSA呈显著负相关。研究结果显示,在氯代烃污染地下水规模化治理中进行药剂设计时,应首选杂质含量较低的铁还原颗粒,且适宜添加量的mZVI在成本和表面利用率方面更具优势。

     

    Abstract: Iron reduction particles, represented by zero-valent iron (ZVI), are widely used in the remediation of contaminated groundwater of chlorinated hydrocarbon. However, the reactivity towards refractory saturated chlorinated hydrocarbons and dominant influencing factors remain unexplored. Contaminated groundwater with high concentration of chlorinated ethane from an abandoned organic solvent plant in North China was collected, and the chemical reduction activities of four particle sizes (100 mesh, 200 mesh, 400 mesh, 800 mesh) of micro-scale zero-valent iron (mZVI), nano-scale zero-valent iron (nZVI) and pyrite on 1,1,2-trichloroethane (1,1,2-TCA) in the actual contaminated groundwater were comprehensively evaluated. The factors and laws affecting the reactivity of iron reduction particles were revealed by redundancy and correlation analysis. The results showed that the pseudofirst-order rate constant (kobs) and mass normalized rate constants (kM) of 1,1,2-TCA in nZVI reaction group were the highest, reaching 0.012 5 d−1 and 0.008 L/(g·d), respectively, followed by mZVI, and the reduction of pyrite was the weakest. Although the increase of particle dosage could improve the degradation rate of 1,1,2-TCA, the reaction rate per unit mass decreased. However, contrary to traditional cognition, the specific surface area normalized rate constant (kSA) was more dominant for mZVI, and the kSA of 200 mesh mZVI was 22 times that of nZVI under the same additive quantity. Redundancy analysis showed that the content of impurities such as S, O, Cl, C and the dosage of particles restricted kobs and kM, while the content of O, C, S and specific surface area were most correlated with kSA, and correlation analysis showed that O, C, specific surface area and kSA were significantly negatively correlated. The results show that iron reduction particles with lower impurity content should be preferred in the design of the large-scale treatment of groundwater polluted by chlorinated hydrocarbons, and the appropriate amount of mZVI is more advantageous in terms of cost and surface utilization.

     

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