This study investigated the direct and indirect electro-oxidation of amine-containing pharmaceuticals (acetaminophen (ACT), diclofenac (DIC), and sulfamethoxazole (SMX)) by using graphite electrodes, and to compare the influence by using different electrolytes (Na2SO4 and NaCl). Under the optimum conditions of current (I) at 0.5 A, in direct system, 74.3%, 90.0%, 81.6% of ACT, DIC, and SMX were respectively removed after 60 min (k = 0.023, 0.037, 0.027 min−1), 48.9%, 85.9%, 68.2% of TOC respectively removed after reaction time. In contrast, at the same current intensity, in indirect system, ACT, DIC, and SMX were eliminated within 30 min (k = 0.117, 0.307, 0.170 min−1), 89.6%, 92.6%, 99.6% of TOC respectively removed after reaction time. The results indicated that the dissociated compounds were attracted to the anode due to electrostatic forces and had higher mass transformation rates in the direct electro-oxidation process. According to the cyclic voltammogram, indirect oxidation occurred when active chlorine species were generated from chloride ions anodically to destroy pollutants. Based on intermediates detected during electro-oxidation treatment by ultra performance liquid chromatography-quadrupole time-of-flight mass spectrometry (UPLC-Q-TOF-MS), only oxidized intermediates were found in the direct oxidation system, while both oxidized and chlorinated intermediates were found in the indirect oxidation system.
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