Degradation of pharmaceutical compounds in water by oxygenated electrochemical oxidation: Parametric optimization, kinetic studies and toxicity assessment.

The pharmaceutical compounds sulfamethoxazole (SMX), propranolol (PRO) and carbamazepine (CBZ) are biorecalcitrant and frequently detected in waters causing negative impacts on human health and aquatic organisms. Electrochemical oxidation appears as an effective option for the removal of recalcitrant compounds and its enhancement is an important issue for the removal of emerging compounds in water. The contribution of this research lies in the comprehensive analysis of the oxygenated electro chemical oxidation of CBZ, SMX and PRO using Nb/BDD mesh anode. The effect of treatment time, current, pH and oxygen injection on the SMX, PRO and CBZ degradation was assessed using Na2SO4 as electrolyte, process optimization was performed, by-products were identified, kinetic and toxicity tests were carried out using different electrolytes. Finally, the process effectiveness was tested using real secondary effluent spiked with the mixture of the pharmaceutical compounds and the acute toxicity was determined. The obtained results indicated that the oxygenated electrochemical oxidation allows effective simultaneous SMX, PRO and CBZ degradation, which showed a significant dependence of treatment time, current and oxygen injection in Na2SO4 electrolyte. At 90 min of electrolysis the parent compounds were detected as well as eight by-products. At 150 min of treatment, further to the already determined by-products and the parent compounds, appeared phenol and p-benzoquinone. Based on the identified compounds, degradation pathways were explained as a result of two main mechanisms: transformation (hydroxylation, deamination, desulfunation) and bond rupture. The kinetic study indicated an increase of the first-order kinetic constant in the oxygenated electrochemical oxidation process using Na2SO4 and NaBr as electrolyte, nevertheless the constant decreased in the presence of NaCl. In the assays with secondary effluent spiked with SMX, PRO and CBZ, the oxygenation did not enhance the performance of the process, however; pharmaceuticals were degraded with a higher removal rates compared with the ones determined in the Na2SO4 synthetic solutions assays; the oxygenation enhanced the TOC and COD removal. The acute toxicity of spiked secondary effluent was reduced from the first few minutes of the electrochemical oxidation process.