Heavy metal-organic complex wastewater is one of the most important problems in industrial wastewater treatment due to its difficult biodegradation. This work proposed, for the first time, to use ferrous hydroxyl complex (FHC) , which had stronger reduction and complexation abilities, to degrade Cu(Ⅱ)-EDTA to remove copper, The generated CuFe_2O_4, Cu_2O, and other active metals were then used in situ to catalyze the generation of ·OH from O_3 to promote the complete mineralization of organie ligands, ultimately achieving the simultaneous removal of heavy metals and organic ligands. Under optimal conditions, when the [Fe^2+] : [OH^-] ratio of FHC was 1 : 3, the dosage was 2 mmol/L, and the O_3 dose was 10 mg·min^-1, copper and organic ligands in 0.2 mmol/L, Cu(Ⅱ)-EDTA could be completely removed in 1 h, and no residual iron was present. When the ratio of [ FHC (1 : 3)]:[Cu( Ⅱ)-EDTA] was higher than 5 : 1, complete copper removal was ensured. Furthermore, the economic efficiency of Cu(Ⅱ)-EDTA complexation removal could be enhanced by preferentially inereasing the ratio of [OH^-] in the FHC rather than the amount of FHC dosed. The system was not affected by Cl-, NO_3^-, SO_4^2-, and other common anions in the wastewater, demonstrating strong resistance to environmental interference. The CuFe_2O_4, and Cu_2O generated in situ after complex breakdown, as well as the Fe_3O_4 formed after catalytic ozonation, were magnetic and had the potential for magnetic separation. The EPR results confirmed that the in-situ generated products promoted the production of ·OH, 1^O_2 and ·O^-2, from O_3. The quenching results, showing a decrease in EDTA removal from 100% to 57.7% after TBA addition, indicated that ·OH was involved in EDTA degradation. Based on the LC-MS analysis , it was demonstrated that FHC broke Cu(Ⅱ)-EDTA to form Fe-EDTA, and that after the O_3 addition, the N-C bond in Fe-EDTA was broken by  ·OH and O_3. Successive decarboxylation formed the intermediates such as Fe-ED3A, Fe-ED2A, glycine, Fe-NTA, and NTA , or further acetate group substitution to form Fe-IMDA and IMDA, which were ultimately mineralized to CO_2 and H_2O. The process is of importance for heavy metal-organic complex wastewater treatment.

重金属-有机络合物废水因其难以被生物降解，是工业废水治理的重要难题之一。首次提出采用还原和络合能力更强的多羟基结构态亚铁（FHC）还原破络Cu（Ⅱ）-EDTA以去除铜。利用原位生成的CuFe_2O_4、Cu_2O等活性金属催化臭氧（O_3）生成·OH，促进有机配体的完全矿化，最终实现重金属和有机配体的同步去除。在优化条件下，当FHC的[Fe^2+]∶[OH^-]配比为1∶3，投加量为2 mmol/L,O_3剂量为10 mg·min-1时，可在60 min内将0.2 mmol/L Cu（Ⅱ）-EDTA中的铜和有机配体完全去除，且无残留铁存在。当[FHC（1∶3）]∶[Cu（Ⅱ）-EDTA]高于5∶1时，可确保铜被完全破络去除，并且通过提高FHC中[OH-]的比例，而非增加FHC投加量，可以提高Cu（Ⅱ）-EDTA破络去除的经济性。研究表明，该工艺不受Cl-、NO_3^-、SO_4^2-等常见阴离子的影响，具备良好的抗环境干扰能力。破络后原位生成的CuFe_2O_4、Cu_2O以及臭氧催化氧化后形成的Fe_3O_4均具有磁性，具备磁力分离的潜力。电子自旋共振（EPR）结果证实了原位生成产物可催化O_3产生·OH、1^O_2和·O^-2。淬灭实验结果显示，加入叔丁醇（TBA）后EDTA的去除率从100.0%降至57.7%，间接证明·OH参与了EDTA的降解。基于LC-MS的分析结果证明，FHC还原破络Cu（Ⅱ）-EDTA形成乙二胺四乙酸铁（Fe-EDTA），通入O_3后，Fe-EDTA中的N—C键被·OH和O_3破坏，连续脱羧形成三乙酸乙二胺铁（Fe-ED3A）、二乙酸乙二胺铁（Fe-ED2A）、甘氨酸、次氮基三乙酸铁（Fe-NTA）和次氮基三乙酸（NTA）等中间产物，或进一步通过乙酸基团取代形成亚胺二乙酸铁（Fe-IMDA）和亚胺二乙酸（IMDA），并最终矿化为CO_2和H_2O。该技术对于重金属-有机络合物废水治理具有借鉴参考意义。