The role of effluent nitrate in trace organic chemical oxidation during UV disinfection

Most conventional biological treatment wastewater treatment plants (WWTPs) contain nitrate in the effluent. Nitrate undergoes photolysis when irradiated with ultraviolet (UV) light in the 200-240 and 300-325 nm wavelength range. In the process of nitrate photolysis, nitrite and hydroxyl radicals are produced. Medium pressure mercury lamps emitting a polychromatic UV spectrum including irradiation below 240 nm are becoming more common for wastewater disinfection. Therefore, nitrified effluent irradiated with polychromatic UV could effectively become a de facto advanced oxidation (hydroxyl radical) treatment process. UV-based advanced oxidation processes commonly rely on addition of hydrogen peroxide in the presence of UV irradiation for production of hydroxyl radicals. This study compares the steady-state concentration of hydroxyl radicals produced by nitrate contained in a conventional WWTP effluent to that produced by typical concentrations of hydrogen peroxide used for advanced oxidation treatment of water. The quantum yield of hydroxyl radical production from nitrate by all pathways was calculated to be 0.24 ± 0.03, and the quantum yield of hydroxyl radicals from nitrite was calculated to be 0.65 ± 0.06. A model was developed that would estimate production of hydroxyl radicals directly from nitrate and water quality parameters. In effluents with >5 mg-N/L of nitrate, the concentration of hydroxyl radicals is comparable to that produced by addition of 10 mg/L of H₂O₂. Nitrifying wastewater treatment plants utilizing polychromatic UV systems at disinfection dose levels can be expected to achieve up to 30% degradation of some micropollutants by hydroxyl radical oxidation. Increasing UV fluence to levels used during advanced oxidation could achieve over 95% degradation of some compounds.