RESUMO
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 90â¯min of electrolysis the parent compounds were detected as well as eight by-products. At 150â¯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.
Assuntos
Técnicas Eletroquímicas , Preparações Farmacêuticas/análise , Poluentes Químicos da Água/análise , Purificação da Água/métodos , Cinética , Oxirredução , Preparações Farmacêuticas/química , Poluentes Químicos da Água/químicaRESUMO
The biodegradation of fluoxetine, mefenamic acid, and metoprolol using ammonium-nitrite-oxidizing consortium, nitrite-oxidizing consortium, and heterotrophic biomass was evaluated in batch tests applying different retention times. The ammonium-nitrite-oxidizing consortium presented the highest biodegradation percentages for mefenamic acid and metoprolol, of 85 and 64% respectively. This consortium was also capable to biodegrade 79% of fluoxetine. The heterotrophic consortium showed the highest ability to biodegrade fluoxetine reaching 85%, and it also had a high potential for biodegrading mefenamic acid and metoprolol, of 66 and 58% respectively. The nitrite-oxidizing consortium presented the lowest biodegradation of the three pharmaceuticals, of less than 48%. The determination of the selected pharmaceuticals in the dissolved phase and in the biomass indicated that biodegradation was the major removal mechanism of the three compounds. Based on the obtained results, the biodegradation kinetics was adjusted to pseudo-first-order for the three pharmaceuticals. The values of k biol for fluoxetine, mefenamic acid, and metoprolol determined with the three consortiums indicated that ammonium-nitrite-oxidizing and heterotrophic biomass allow a partial biodegradation of the compounds, while no substantial biodegradation can be expected using nitrite-oxidizing consortium. Metoprolol was the less biodegradable compound. The sorption of fluoxetine and mefenamic acid onto biomass had a significant contribution for their removal (6-14%). The lowest sorption coefficients were obtained for metoprolol indicating that the sorption onto biomass is poor (3-4%), and the contribution of this process to the global removal can be neglected.
Assuntos
Fluoxetina/análise , Ácido Mefenâmico/análise , Metoprolol/análise , Consórcios Microbianos , Poluentes Químicos da Água/análise , Biodegradação Ambiental , Reatores Biológicos , Processos Heterotróficos , Cinética , Oxirredução , EsgotosRESUMO
The removal of two blood lipid regulators, clofibric acid (CLA) and gemfibrozil (GFZ), was evaluated using two identical aerobic membrane bioreactors with 6.5 L effective volume each. Polysulfone ultrafiltration hollow fiber membranes were submerged in the reactors. Different operating conditions were tested varying the organic load (F/M), hydraulic residence time (HRT), biomass concentration measured as total suspended solids in the mixed liquor (MLTSS) and the sludge retention time (SRT). Complete GFZ removal was obtained with F/M of 0.21-0.48 kg COD kgTSS⻹ d⻹, HRT of 4-10 hours, SRT of 10-32 d and MLTSS of 6-10 g L⻹. The GFZ removal can be attributed to biodegradation and there was no accumulation of the compound in the biomass. The CLA removals improved with the SRT and HRT increase and F/M decrease. Average removals of 78-79% were obtained with SRT 16-32 d, F/M of 0.21-0.34 kgCOD kgTSS⻹ d⻹, HRT of 7-10 hours and MLTSS of 6-10 g L⻹. Biodegradation was found to be the main removal pathway.