Optimizing radical yield from free chlorine with tailored UV light emitting diode emission spectra

Novel UV sources, which do not contain mercury, provide the opportunity for enhancement of current oxidation technologies through spectral optimization, minimizing inefficiencies that currently limit conventional technology. Wastewater reuse is the primary full-scale application of UV advanced oxidation processes (AOPs) in practice but any background absorbance and the low molar absorption by conventional radical promoters (hydrogen peroxide) have historically limited their system efficiency, resulting in the underutilization of photons in a reactor. This bench-scale research evaluated use of longer wavelength UV light emitting diodes (265, 280, and 300 nm) matched with free chlorine to optimize the utilization of photons for advanced oxidation. Free chlorine possesses large absorption bands in the 280 to 300 nm range in basic pH waters which are common in carbon-based reuse and was used to experimentally verify quantum yields of hydroxyl radical generation across the UV LED peak emission wavelengths. pH- and wavelength-dependent fluence-based rate constants were experimentally derived using Nitrobenzene and Benzoic acid as probe compounds and evaluated to determine the contribution of the hydroxyl and chlorine radical. Reclaimed water taken from various advanced treatment steps was treated with this UV LED AOP to investigate how background absorbance affects radical generation and contaminant transformation kinetics. In addition, alternative performance metrics to evaluate hydroxyl radical production at different incident fluence rates and different rates of photon absorption at unique wavelengths across varying background UV absorbance levels were assessed.