Electrochemical combustion of herbicide mecoprop in aqueous medium using a flow reactor with a boron-doped diamond anode

The anodic oxidation of 1.8l of solutions with mecoprop (2-(4-chloro-2-methylphenoxy)-propionic acid or MCPP) up to 0.64 g l(-1) in Na2SO4 as background electrolyte within the pH range 2.0-12.0 has been studied using a flow plant containing a one-compartment filter-press electrolytic reactor with a boron-doped diamond (BDD) anode and a stainless steel cathode, both of 20-cm2 area. Electrolyses carried out in batch under steady conditions and operating at constant current density between 50 and 150 mA cm(-2) always yield complete mineralization due to the great concentration of hydroxyl radical generated at the BDD anode. The degradation rate is practically independent of pH and Na2SO4 concentration, but it becomes faster with increasing MCPP concentration, current density, temperature and liquid flow rate. The effect of these parameters on current efficiency and energy cost has also been investigated. Generated weak oxidants such as H2O2 and peroxodisulfate ion have little influence on the mineralization process. The kinetics for the herbicide decay follows a pseudo first-order reaction with a higher rate constant when current density increases. Aromatic products such as 4-chloro-o-cresol, 2-methylhydroquinone and 2-methyl-p-benzoquinone, and generated carboxylic acids such as maleic, fumaric, lactic, pyruvic, tartronic, acetic and oxalic, have been identified as intermediates by chromatographic techniques. The initial chlorine is completely released in the form of chloride ion, which is slowly oxidized to Cl2 at the BDD anode. A reaction pathway for MCPP mineralization involving all products detected is proposed.