Decomplexation of Cr(III)-EDTA and simultaneous abatement of total Cr by photo-oxidation: efficiency and in situ reduction of intermediate Cr(VI)

Most prevailing processes are incapable of removing Cr(III)-organic complexes efficiently and facing the problem of in-process formation of highly toxic Cr(VI) based on oxidation. The efficient decomplexation of Cr(III) complexes and simultaneous abatement of Cr with low Cr(VI) accumulation would be desirable in treatment of Cr(III)-complexed wastewater. Here, we found efficient degradation of Cr(III)-EDTA and simultaneous removal of Cr by forming Cr₂O₃ precipitate from simulated solution as well as an electroplating effluent under UV irradiation. The results showed a complete degradation of Cr(III)-EDTA after reaction time of 60 min and 70–80% of TOC mineralization within 180 min as well. About 90% of Cr(III) precipitated as Cr₂O₃ simultaneously, with the residual total Cr below 1.5 mg/L. The degradation of Cr(III)-EDTA was a stepwise de-acetate group process, as proven by the obvious attenuation of peaks related to carboxyl groups and C–C bond from FT-IR spectra of Cr(III)-EDTA and significant mineralization of TOC after UV irradiation. Based on negligible accumulation of Cr(VI) (less than 0.1 mg/L) under N₂-sparged condition, the C-centered radicals from the β-fragmentation of O-centered radicals formed by photo-induced ligand-to-metal charge transfer were responsible for the in situ reduction of intermediate Cr(VI), resulting in the low accumulation of Cr(VI). The addition of 20 mg/L Fe²⁺ was capable of removing the remaining Cr(VI) and total Cr, with Cr(VI) and total Cr less than 0.1 and 1.0 mg/L, respectively. Moreover, the photo-oxidation process combined with Fe²⁺ addition were efficient in removing other Cr(III) complexes, such as Cr(III)-citrate and those from a realistic electroplating effluent. We believe that this study would provide an alternative option for efficient degradation of Cr(III) complexes and simultaneous abatement of Cr from contaminated water.