A novel system coupling an electro-Fenton process and an advanced biological process to remove a pharmaceutical compound, metronidazole.

The objective of this study was to improve the mineralization of metronidazole, a recalcitrant antibiotic by the development of a new combined process coupling electro-Fenton and a biological process. For biotreatment, various strategies were considered bioaugmentation, bioacclimatation and biostimulation alone or combined. So, the novelty of this strategy is to combine advanced oxidation process with advanced biological process. The conventional biotreatment with activated sludge after 120 h of culture, led to 58.1% mineralization, whereas the pure isolated strains, from activated sludge culture in the presence of metronidazole by-products, identified as Pseudomonas putida (strain A) and Achromobacter sp. (strain B), led to 37.2% and 40.1% respectively. After original acclimation of the isolated strains to electrolysis by-products, the mineralization levels reached 75.6% and 72.9% for strains A and B respectively after 120 h of culture. The results showed that the mineralization of metronidazole by-products was the most important in the case of the combination of autochthonous bioaugmentation and biostimulation, with 96.1% after 120 h of treatment. By coupling the two processes, the global treatment reached therefore a mineralization yield of 97% with a reduction in processing time of 16 days compared to previous conventional biological treatment.

Metronidazole removal by means of a combined system coupling an electro-Fenton process and a conventional biological treatment: By-products monitoring and performance enhancement.

In order to mineralize Metronidazole (MTZ), a process coupling an electro-Fenton pretreatment and a biological degradation was implemented. A mono-compartment batch reactor containing a carbon-felt cathode and a platinum anode was employed to carry out the electro-Fenton pretreatment of MTZ. A total degradation of MTZ (100 mg L-1) was observed at 0.07 mA.cm-2 after only 20 min of electrolysis. Yet, after 1 and 2 h of electrolysis, the mineralization level remained low (16.2% and 32% respectively), guaranteeing a significant residual organic content for further biological treatment. LCMS/MS was used to determine the intermediates by-products and hence to propose a plausible degradation pathway. An increase from 0 to 0.44 and 0.6 for 1 and 2 h of electrolysis was observed for the BOD5/COD ratio. Thus, from 1 h of electro-Fenton pretreatment, the electrolysis by-products were considered biodegradable. A biological treatment of the electrolysis by-products after 1 and 2 h was then realized. The mineralization yields reached very close values, about 84% for 1 and 2 h of electrolysis after 504 h of biological treatment, namely close to 89% for the overall process, showing the pertinence of the proposed coupled process.

Reactive oxygen and iron species monitoring to investigate the electro-Fenton performances. Impact of the electrochemical process on the biodegradability of metronidazole and its by-products.

In this study, the monitoring of reactive oxygen species and the regeneration of the ferrous ions catalyst were performed during electro-Fenton (EF) process to highlight the influence of operating parameters. The removal of metronidazole (MTZ) was implemented in an electrochemical mono-compartment batch reactor under various ranges of current densities, initial MTZ and ferrous ions concentrations, and pH values. It was found that under 0.07 mA cm-2, 0.1 mM of ferrous ions and pH = 3, the efficiency of 100 mg L-1 MTZ degradation and mineralization were 100% within 20 min and 40% within 135 min of electrolysis, respectively. The highest hydrogen peroxide and hydroxyl radical concentrations, 1.4 mM and 2.28 mM respectively, were obtained at 60 min electrolysis at 0.07 mA cm-2. Improvement of the biodegradability was reached from 60 min of electrolysis with a BOD5/COD ratio above 0.4, which was reinforced by a respirometric study, that supports the feasibility of coupling electro-Fenton and biological treatment for the metronidazole removal.