Photocatalytic degradation of DOM in urban stormwater runoff with TiO₂ nanoparticles under UV light irradiation: EEM-PARAFAC analysis and influence of co-existing inorganic ions

In situ photocatalytic degradation of dissolved organic matter (DOM) of stormwater runoff can efficiently improve the aquatic environment quality and relieve the wastewater treatment pressure. In this work, photocatalytic degradation of DOM in TiO₂ (AEROXIDE^® P-25) photocatalyst under illumination of ultraviolet (UV) light was carried out, considering the influence of various factors like TiO₂ dosage, solution pH along with the existence of co-existing ions (Cu²⁺ and H₂PO₄ ⁻). Generally, the variations of dissolved organic carbon (DOC), UV-based parameters and peak intensities of fluorescent constituents with UV exposure time fitted perfectly with the pseudo-first-order kinetics model. The total DOM removal efficiency was affected by diversiform factors like adsorption capacity of TiO₂, UV light utilization efficiency, reactive free radicals produced and the influence of co-existing ions. The results of fluorescence excitation-emission matrix (EEM) coupled with parallel factor analysis (PARAFAC) modeling demonstrated that all the photodegradation rates for three identified fluorescent constituents (protein-like constituent 1 and 3, humic-like constituent 2) were faster than UV-absorbing chromophores, suggesting the DOM molecules in urban stormwater runoff contained much more π*-π transition structures. In addition, H₂PO₄ ⁻ ions affected the photodegradation of DOM by capturing positive holes (h⁺) and hydroxyl radical (·OH), whereas Cu²⁺ ions were inclined to generate Cu-protein complexes that were more difficult to degrade than the other Cu-DOM complexes. This study supplied novel insights into the photocatalytic degradation mechanism of individual organic constituent in urban stormwater runoff and explored the influences of co-existing contaminants on their adsorption-photocatalysis processes. It is essential to clarify the photocatalytic DOM degradation behaviors and the influence of co-existing ions in urban stormwater runoff with the aid of EEM-PARAFAC.