Degradation of 4-aminoantipyrine by elecro-oxidation with a boron-doped diamond anode: optimization by central composite design, oxidation products and toxicity

Electro-oxidation with electrogenerated H2O2 (EO-H2O2) was applied to treat acidic aqueous solutions of 4-aminoantipyrine (4-AA), a persistent drug metabolite of dipyrone, in sulfate medium. Trials were made using a boron-doped diamond anode in the presence of H2O2 electrogenerated on site. A 24 central composite design (CCD) was employed to evaluate the effect of four independent variables, namely current density (j), pH, 4-AA concentration and electrolysis time, on the percentages of degradation and mineralization, as well as on mineralization current efficiency (MCE). Predicted responses agreed with observed values, showing linear trendlines with good R2 and R2adj values. The degradation was optimum at j = 77.5 mA cm-2, pH 3.5 and 62.5 mg L-1 4-AA, leading to 63% and 99% removal after 3 and 7 min, respectively. For those solutions, the largest mineralization was found at j = 77.5 mA cm-2, attaining 45% abatement at 175 min. Low MCE values were obtained in all electrolyses. An initial route for 4-AA degradation is proposed based on one dimer and eleven aromatic and aliphatic intermediates detected in the treated solutions at pH 3.5 by LC-MS. The initial 62.5 mg L-1 solution at pH 3.5 presented acute toxicity on Artemia salina larvae, with LC50 = 13.6 mg L-1, being substantially reduced after 3 and 7 min of EO-H2O2 at j = 77.5 mA cm-2 due to the formation of less toxic derivatives