Unintended polyhalogenated carbazole production during advanced oxidation of coking wastewater

Polyhalogenated carbazoles (PHCZs) are emerging as dioxin-like global pollutants, yet their environmental origins are not fully understood. This study investigates the application of the Fenton process in coking wastewater treatment, focusing on its dual role in carbazole removal and unintended PHCZ formation. The common halide ions (Cl^- and Br^-) in coking wastewater, especially Br^- ions, exerted a notable impact on carbazole removal. Particularly, the influence of Br^- ions was more significant, not only enhancing carbazole removal but also shaping the congener composition of PHCZ formation. Elevated halide ion concentrations were associated with the heightened formation of higher halogenated carbazoles. The Fenton reagent dosage ratio was identified as a crucial factor affecting the congener composition of PHCZs and their toxic equivalency value. The coexisting organic substance (i.e., phenol) in coking wastewater was observed to inhibit PHCZ formation, likely through competitive reactions with carbazole. Intriguingly, ammonium (NH₄⁺) facilitated the generation of higher and mixed halogenated carbazoles, possibly due to the generation of nitrogen-containing brominating agents with stronger bromination capacity. This study underscores the importance of a comprehensive assessment, considering both substrate removal and potential byproduct formation, when employing the Fenton process for saline wastewater treatment.