Role of Antioxidant Moieties in the Quenching of a Purine Radical by Dissolved Organic Matter

Dissolved organic matter (DOM) has been known to inhibit the degradation of trace organic contaminants (TrOCs) in advanced oxidation processes but quantitative understanding is lacking. Adenine (ADN) was selected as a model TrOC due to the wide occurrence of purine groups in TrOCs and the well-documented transient spectra of its intermediate radicals. ADN degradation in the presence of DOM during UV/peroxydisulfate treatment was quantified using steady-state photochemical experiments, time-resolved spectroscopy, and kinetic modeling. The inhibitory effects of DOM were found to include competing for photons, scavenging SO₄^•- and HO^•, and also converting intermediate ADN radicals (ADN(-H)^•) back into ADN. Half of the ADN(-H)^• were reduced back to ADN in the presence of about 0.2 mg_C L^-1 of DOM. The quenching rate constants of ADN(-H)^• by the 10 tested DOM isolates were in the range of (0.39-1.18) × 10⁷ M_C^-1 s^-1. They showed a positive linear relationship with the total antioxidant capacity of DOM. The laser flash photolysis results of the low-molecular-weight analogues of redox-active moieties further supported the dominant role of antioxidant moieties in DOM in the quenching of ADN(-H)^•. The diverse roles of DOM should be considered in predicting the abatement of TrOCs in advanced oxidation processes.