Comparative Study for Interactions of Sulfate Radical and Hydroxyl Radical with Phenol in the Presence of Nitrite

Sulfate radical (SO₄^•-)- and hydroxyl radical (HO^•)-based advanced oxidation processes (AOPs) are effective for the removal of organic pollutants in water treatment. This study compared the interactions of SO₄^•- and HO^• for the transformation of phenol in UV/peroxydisulfate (PDS) and UV/H₂O₂ with the presence of NO₂^-, which is widely present in aquatic environments and transforms SO₄^•- and HO^• to ^•NO₂. By using laser flash photolysis, the products of phenol reacting with SO₄^•- and HO^• were demonstrated to be phenoxy radical and phenol-HO-adduct radical, respectively. This result, along with density functional theory (DFT) calculations, indicate that the predominant reaction mechanisms of phenol with SO₄^•- and HO^• with phenol are electron transfer and addition, respectively. The different mechanisms induced the much higher formation of nitrophenols by SO₄^•- than HO^• in the presence of NO₂^- through the fast combination of phenoxy radicals and ^•NO₂. The conversion yields of phenol to nitrophenols (including 2-nitrophenol and 4-nitrophenol), were 47.5% by SO₄^•- versus 5.3% by HO^• at the experimental conditions. Increasing PDS/H₂O₂ dosages from 0.2 to 1 mM resulted in a 61.9% increase of nitrophenol conversion yield in UV/PDS/NO₂^- but a 35.4% decrease of that in UV/H₂O₂/NO₂^-. In addition, the significant formation of phenoxy radicals by SO₄^•- also induced many nitrated polymers in UV/PDS/NO₂^-, while those induced in UV/H₂O₂/NO₂^- were negligible. The significant formation of nitrophenols and nitrated polymers increased the mutagenicity by 860.5% when the removal rate of phenol was 98% by UV/PDS/NO₂^-. This is the first study to demonstrate the different mechanisms of phenol transformation by SO₄^•- and HO^• in the presence of NO₂^-.