Enhanced formation of chlorinated disinfection byproducts in the UV/chlorine process in the presence of benzophenone-4

Benzophenone-4 (BP4) is UV-filter that is widely in sunscreens and cosmetics to prevent skin damage from sunlight exposure. Washing off of BP4 from the human body in swimming pools represents a direct source of BP4 in the environment. In this study, we investigated the transformation of BP4 by free chlorine, chloramine, and UV/chlorine, which can be found in swimming pool water. It was found that BP4 can be rapidly removed by both chlorine and chloramine treatment, but only chlorination led to appreciable formation of chlorinated disinfection by-products (DBPs), such as dichloroacetic acid and trichloroacetic acid. However, chloramination of BP4 resulted in higher levels of chlorinated intermediates, which were relatively recalcitrant to further chlorination. The UV/chlorine process was significantly more efficient than the chlorine treatment alone for BP4 removal and resulted in trace chlorinated intermediates and formation of DBPs. Radical scavenger tests revealed that the removal of BP4 in the UV/chlorine process was mostly ascribed to reactions with the Cl and OH generated from HClO photolysis. The presence of methanol as a radical scavenger resulted in incomplete removal of BP4 in the UV/chlorine process and enhanced the formation of DBPs. The increase in DBP formation was because the residual BP4 can be exited to a triplet state (3BP4∗) upon UV irradiation. 3BP4∗ subsequently reacted with O2 to form 1O2, a reactive oxygen species that generated DBPs by reacting with chlorinated intermediates in water. All benzophenone-type UV-filters may have similar photochemical activity and thus influence the transformation of other organics in sunlit surface water environments.