Electrochemical degradation of PAH compounds in process water: A kinetic study on model solutions and a proof of concept study on runoff water from harbour sediment purification

The present study has investigated the possibility to apply electrochemical oxidation in the treatment of polycyclic aromatic hydrocarbon (PAHs) pollutants in water. The reaction kinetics of naphthalene, fluoranthene, and pyrene oxidation have been studied in a batch recirculation experimental setup applying a commercial one-compartment cell of tubular design with Ti/Pt₉₀-Ir₁₀ anode. The rate of oxidation has been evaluated upon variations in current density, electrolyte composition and concentration. All three PAHs were degraded by direct anodic oxidation in 0.10 M Na₂SO₄ electrolyte, and the removal rates were significantly enhanced by a factor of two to six in 0.10 M NaCl due to contribution from the indirect hypochlorite oxidation. Second order reaction kinetics was observed for the degradation of naphthalene in all electrolytes whereas fluoranthene and pyrene followed first order kinetics. Decreased current densities from 200 to 15 mA cm^-2 in the NaCl electrolyte also decreased the removal rates, but significantly enhanced the current efficiencies of the PAH oxidation, based on a defined current efficiency constant, k_q. This observation is believed to be due to the suppression of the water oxidation side reaction at lower applied voltages. A proof of concept study in real polluted water demonstrated the applicability of the electrochemical oxidation technique for larger scale use, where especially the indirect chloride mediated oxidation approach was a promising technique. However, the risk and extent of by-product formation needs to be studied in greater detail.