Underwater bubbling plasma assisted with persulfate activation for the synergistic degradation of tetracycline hydrochloride

Abstract

The performance and mechanism of persulfate consisting of peroxymonosulfate (PMS) and peroxydisulfate (PDS) activation by underwater bubbling plasma (UBP) for the synergistic removal of tetracycline hydrochloride (TCH) were comparatively investigated. Both PMS and PDS addition significantly promoted the removal of TCH in UBP system, indicating persulfate exhibited highly synergistic effect with UBP. Furthermore, enhancing the persulfate dosage, peak voltage and pulse frequency, as well as reducing initial TCH concentration were favorable for the elimination of TCH. Compared with neutral condition, acidic and alkaline condition were advantageous to TCH removal. The presence of coexisting substances including Cl−, SO42− and humic acid (HA) had an adverse effect on TCH degradation, while Fe2+ could improve the removal of TCH. The degradation of ciprofloxacin and metronidazole proved the applicability for other antibiotics degradation of the reaction system. SO4−·, ·OH, ·O2−, hydrated electrons, O3 and H2O2 were the active substances responsible for TCH removal. The reduction of aqueous O3 concentration and enhancement of H2O2 concentration were observed after persulfate addition. UV–vis spectra and TOC analysis illustrated the addition of PMS or PDS facilitated the degradation and mineralization of TCH. 3D-EEMF spectra visually displayed the degradation process of TCH. Plausible degradation routes were deduced based on LC-MS and the toxicities of TCH and its intermediates were evaluated by Toxicity Estimation Software Tool.