AbstractA biofilm airlift suspension (BAS) reactor and an undivided flow cell equipped with a boron‐doped diamond (BDD) anode and a stainless‐steel cathode were used to investigate the effects of varying operating conditions on process performance in the biological and electrochemical oxidation of a mixture of naphthalenesulfonates contained in the infiltration water of a contaminated industrial site. The experiments were aimed at evaluating the feasibility of process integration and the criteria for optimization (i.e. how to maximize degradation efficiency with minimum energy consumption) in combined biological and electrochemical oxidation of scarcely biodegradable compounds. Because of high reactor biomass concentration and long biomass retention time, the BAS reactor achieved a high degradation capacity (up to 6.8 kg COD m−3 d−1). On the other hand, owing to the recalcitrant character of some of the aromatic sulfonates in the leachate, the overall degradation efficiency did not exceed 70% based on COD measurements. All naphthalene‐mono‐ and ‐disulfonates (except naphthalene‐1,5‐disulfonate) were completely degraded in the BAS reactor, whereas more complex molecules (e.g. naphthalenetrisulfonates) were more recalcitrant to biological oxidation. These compounds were completely mineralized by electrochemical oxidation using a boron‐doped diamond anode. The energy consumption and the time required for the complete mineralization of the infiltration water decreased from 80 kWh m−3 and 4 h to 61 kWh m−3 and 3 h for the oxidation of raw and biologically pretreated leachate, respectively. Copyright © 2005 Society of Chemical Industry