Photocatalytic ozonation of offshore produced water by TiO2 nanotube arrays coupled with UV-LED irradiation

Offshore produced water (OPW) containing hazardous substances such as polycyclic aromatic hydrocarbons (PAHs) needs to be treated prior to discharge. This study integrated a photocatalytic ozonation system with TiO2 nanotube arrays (TNA) and UV-light-emitted diode (UV-LED) irradiation and applied to treat OPW. Experimental and modeling efforts were made to evaluate the degradation efficiencies of PAHs, examine the behaviors of the OPW composition (e.g., phenols, iodide, and bromide), and investigate the oxidation intermediates and the associated toxicity and biodegradability. The results indicated that ozone significantly enhanced the oxidation rates and removed the PAHs within 30 min, while the TNA showed strong photocatalytic capability. In the early stage, iodide was a strong ozone competitor, accelerating phenol degradation but inhibiting PAH oxidation, whereas UV-LED fortified the effect. The degradation of aromatics was altered by iodide and bromide at different stages. The contributions of four toxicants to the acute toxicity of OPW were quantified and ranked (PAHs > bromoform > phenols > dibromopentane). The EC50 value increased from 3 % to 57 %, and the biodegradability was doubled with less footprint in 28-day biodegradation tests. Overall, it is recommended to sequentially oxidize the matrix of OPW by ozonation and PAHs by the UV-LED/TNA/ozone system.