Full-scale comparison of UV/H2O2 and UV/Cl2 advanced oxidation: The degradation of micropollutant surrogates and the formation of disinfection byproducts

Abstract

The photolysis of chlorine by UV light leads to the formation of the hydroxyl radicals (OH) as well as reactive chlorine species (RCS) that can be effective as advanced oxidation processes (AOPs) for water treatment. Much of the research to date has been done at laboratory- or bench-scale. This study reports results from a model that demonstrates that the relative effectiveness of the UV/Cl₂ AOP compared to the more traditional UV/H₂O₂ AOP is a function of optical path length. As such, the relative effectiveness of the two treatment options evaluated at small scale may not reflect the relative performance at full-scale, making results previously obtained at small-scale potentially less scalable. This study therefore compares the performance of UV/Cl₂ to UV/H₂O₂ at a full-scale water treatment plant, using sucralose and caffeine as spiked surrogates for contaminants that are reactive solely to OH radicals, and to both OH and RCS, respectively. pH was varied between 6.5 and 8.0. The results demonstrated that when using a medium pressure UV lamp, UV/Cl₂ might lead to approximately twice the production of OH radicals as UV/H₂O₂ at pH 6.5 when using the same molar oxidant concentration, but adding chlorine to the UV reactor at pH 8.0 had a negligible impact on OH radical concentration in comparison to UV alone. The study also confirmed previous small-scale results that RCS can be a major contributor to UV/Cl₂ treatment for compounds such as caffeine that are susceptible to RCS, with UV/Cl₂ effective at both pH 6.5 and 8.0 for such compounds. Disinfection byproducts were monitored, with adsorbable organohalide (AOX) formation increasing by approximately 10 μg-Cl/L due to chlorine photolysis, but only at pH 6.5 and not at pH 8.0. This implies that UV/Cl₂ might increase AOX mostly due to reaction between OH and organic precursors to make them more reactive with chlorine, and not due to RCS. The formation of specific DBPs of current or emerging regulatory interest was minimal under all conditions, except for chlorate. Chlorate yields were in the order of 6-18% of the photolysed chlorine.

Keywords: Advanced oxidation; Caffeine; Disinfection byproducts; Sucralose; UV.