Ozone and ozone/vacuum-UV degradation of diethyl dithiocarbamate collector: kinetics, mineralization, byproducts and pathways

The diethyl dithiocarbamate (DDC) collector, a precursor of toxic N-nitrosamines, is detected in flotation wastewaters usually at the ppm level. In this study, the O3 and O3/Vacuum-UV (O3/VUV) processes were compared to investigate the efficient removal of DDC with a low risk of N-nitrosamine formation. The results showed that 99.55% of DDC was removed at 20 min by O3/VUV, and the degradation rate constant was 3.99 times higher than that using O3-alone. The C, S and N mineralization extents of DDC using O3/VUV reached 36.36%, 62.69% and 79.76% at 90 min, respectively. O3/VUV achieved a much higher mineralization extent of DDC than O3-alone. After 90 min of degradation, O3/VUV achieved lower residual concentrations of CS2 and H2S, and released lower amounts of gaseous sulfur byproducts compared to O3-alone. The solid phase extraction and gas chromatography-mass spectrometry (SPE/GC–MS) analysis indicated that the main byproducts in O3/VUV degradation of DDC were amide compounds without the detection of N-nitrosamines. The avoidance of N-nitrosamine formation might be attributed to exposure of UV irradiation and enhanced formation of ˙OH radicals in the O3/VUV system. The degradation pathways of DDC were proposed. This work indicated that O3/VUV was an efficient alternative treatment technique for the removal of DDC flotation collector with low risk of N-nitrosamine formation.