Efficient reductive and oxidative decomposition of haloacetic acids by the vacuum-ultraviolet/sulfite system

Haloacetic acids (HAAs), as a representative category of halogenated disinfection byproducts, are widely detected in disinfected water. In this work, the vacuum ultraviolet (VUV)/sulfite process under N₂ saturated conditions was proposed to eliminate a series of HAAs (i.e., monochloroacetic acid (MCAA), difluoroacetic acid (DFAA), trifluoroacetic acid (TFAA), dichloroacetic acid (DCAA), etc.). The in situ generated hydrated electron (e_aq⁻) demonstrated to be the main species to fulfill the initial degradation and dechlorination of MCAA, while hydroxyl radicals (˙OH) were in charge of the mineralization of MCAA. This means that the VUV/sulfite system is a combination of advanced reduction and oxidation processes (ARPs and AOPs). A significant enhancement of MCAA removal was observed with increasing pH values from 6.0 to 10.0, and surprisingly, k_obs correlated well with the proportion of SO₃^2- as the pH changed. This can be explained by the production of e_aq⁻ from VUV irradiation of SO₃²⁻ rather than HSO₃⁻ and also due to e_aq⁻ being more stable under alkaline conditions. Increasing the sulfite dosage also elevated the degradation of MCAA. However, the addition of certain anions (i.e., chloride (Cl⁻), bicarbonate (HCO₃⁻), and nitrate (NO₃⁻)) and dissolved organic matter (DOM) inhibited the removal of MCAA to varying degrees. The VUV/sulfite system was effective toward various types of halogenated disinfection byproducts, supporting its broad applicability. Nevertheless, even in real waters, the VUV/sulfite system was also promising for the simultaneous abatement of HAAs and other oxyanions.