Comparative electrochemical degradation of salicylic and aminosalicylic acids: Influence of functional groups on decay kinetics and mineralization

Solutions of 100 mL with 1.20 mM of salicylic acid (SA), 4-aminosalicylic acid (4-ASA) or 5-aminosalicylic acid (5-ASA) have been comparatively degraded by anodic oxidation with electrogenerated H₂O₂ (AO-H₂O₂), electro-Fenton (EF) and photoelectro-Fenton (PEF). Trials were carried out with a stirred tank reactor with a BDD anode and an air-diffusion cathode for continuous H₂O₂ production. A marked influence of the functional groups of the drugs was observed in their decay kinetics, increasing in the order SA < 5-ASA < 4-ASA in AO-H₂O₂ and 5-ASA < SA < 4-ASA in EF and PEF, due to the different attack of OH generated at the BDD surface and in the bulk from Fenton's reaction, respectively. This effect was clearly observed when varying the current density between 16.7 and 100 mA cm^-2. The relative mineralization power of the processes always followed the sequence: AO-H₂O₂ < EF < PEF. The three drugs underwent analogous mineralization abatement up to 88% by AO-H₂O₂ at 100 mA cm^-2. The mineralization rate in EF and PEF grew in the order: 4-ASA < 5-ASA < SA. The most powerful process was PEF, attaining >98% mineralization for all the drugs at 100 mA cm^-2. Oxalic and oxamic acids were detected as final short-linear aliphatic carboxylic acids by ion-exclusion HPLC, allowing the fast photolysis of their Fe(III) complexes by UVA light to justify the high power of PEF.