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 mgC 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 MC
–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.