Efficient removal of 3,6-dichlorocarbazole with Fe⁰-activated peroxymonosulfate: performance, intermediates and...

Nowadays, polyhalogenated carbazoles (PHCZs) are a major pollutant that has recently sparked widespread concern. In this work, peroxymonosulfate (PMS) was activated by zero valent iron (Fe⁰) to remove 3,6-dichlorocarbazole (3,6-CCZ). First, the key parameters influencing 3,6-CCZ degradation (PMS dosage, Fe⁰ dosage, initial pH, temperature and co-existing ions) were determined. Under the determined optimum conditions, the removal rate of 3,6-CCZ reached 100% within 1.5 h. Sulfate radicals (SO₄·^-), hydroxyl radicals (OH·), and singlet oxygen (¹O₂) generated in the reaction were directly identified with 0.1 M 5,5-dimethyl-1-pyrrolidine N-oxide (DMPO) by in-situ electron paramagnetic resonance (EPR) and indirectly identified by radical quenching experiments. The main reactive oxygen species (ROS) were different from most reported hydroxyl radicals (OH·) and sulfate radicals (SO₄·^-). In this study, it was found that OH· and ¹O₂ play a major role. Then, fresh and reacted Fe⁰ were characterized by XRD, SEM, and XPS. Iron corrosion products such as Fe₂O₃, Fe₃O₄, and FeOOH were generated. Finally, 3,6-CCZ degradation intermediates were identified by GC-MS and its degradation pathway was speculated. The intermediate pathway confirmed the combined action of (OH·) and (¹O₂) in 3,6-CCZ removal. This study provides new insight into the activation mechanism of Fe⁰-activated PMS and the removal mechanism of 3,6-CCZ.Highlights Fe⁰ is a long-lasting and efficient catalyst of PMS for the degradation of 3,6-CCZ.The key parameters influencing 3,6-CCZ degradation were determined.The degradation pathways of 3,6-CCZ were inferred.OH· and ¹O₂ were the main ROS in Fe⁰-activated PMS system.