Unexpected degradation and deiodination of diatrizoate by the Cu(II)/S(IV) system under anaerobic conditions.

Transition metal catalyzed sulfite auto-oxidation is a promising technology used in water and wastewater treatment for the elimination of contaminants. In the literature, this process has been reported to be efficient only in the presence of oxygen. However, in this study, we unexpectedly found that the degradation of diatrizoate (DTZ) by a system based on the combination of copper ion and sulfite (Cu(II)/S(IV)) reached over 95% under anaerobic conditions, but was considerably retarded under aerobic conditions at pH 7. Furthermore, it was found that Cu(I), generated from the cleavage of the CuSO3 complex, was the main reactive species responsible for the degradation of DTZ by the Cu(II)/S(IV) system under anaerobic conditions. In fact, the absence of oxygen promoted the accumulation of Cu(I). The concomitant release of the iodide ion with the degradation of DTZ indicated that the anaerobic degradation of DTZ by the Cu(II)/S(IV) system mainly proceeded through the deiodination pathway, which was also confirmed by the detection of deiodinated products. The anaerobic degradation of DTZ was favored at higher initial concentrations of Cu(II) or sulfite in this system. Since the CuSO3 complex, the precursor of Cu(I), was formed mainly at pH 7, the highest anaerobic degradation of DTZ was achieved at pH 7. An increase in reaction temperature considerably enhanced the degradation of DTZ by the Cu(II)/S(IV) system with an apparent activation energy of 119.4 kJ/mol. The presence of chloride, bicarbonate and humic acid slightly influenced the anaerobic degradation of DTZ. The experiments with real water samples also demonstrated the effectiveness of the degradation of DTZ by the Cu(II)/S(IV) system under anaerobic conditions.