Enhanced Bioremediation of 4-Chlorophenol by Electrically Neutral Reactive Species Generated from Nonthermal Atmospheric-Pressure Plasma

4-Chlorophenol (4-CP) is a chlorinated aromatic compound with broad industrial applications. It is released into the environment as an industrial byproduct and is highly resistant to biodegradation. Pseudomonas sp. in the environment and activated sludge are used for 4-CP bioremediation; however, the degradation of 4-CP takes a long time. Consequently, the toxicity of 4-CP is a major barrier to its bioremediation. In this study, we investigated the synergistic effect of electrically neutral reactive species on the bacterial bioremediation of 4-CP. Our results showed that the concentration of 4-CP decreased from 2.0 to 0.137 mM and that it was converted to 4-chlorocatechol (4-CC; 0.257 mM), 4-chlororesorcinol (0.157 mM), hydroquinone (0.155 mM), and trihydroxy chlorobenzene and their respective ring-cleaved products following irradiation of neutral reactive species. These compounds were less toxic than 4-CP, except for 4-CC, which reduced the toxicity of 4-CP to Pseudomonas putida. When the neutral reactive species-treated 4-CP fraction was added to P. putida cultured in a synthetic sewage medium for 48 h, the 4-CP concentration was reduced to 0.017 mM, whereas nontreated 4-CP (2.0 mM) was hardly degraded by P. putida. These results suggest that the biodegradation of 4-CP can be efficiently improved by combining irradiation of neutral reactive species with microbial treatment. The irradiation of neutral reactive species of environmental pollutants may additionally lead to further improvements in bioremediation processes.