Hydroxyl radical-induced degradation of fenuron in pulse and gamma radiolysis: kinetics and product analysis

Kovács, Krisztina; Mile, Viktoria; Csay, Tamás; Takács, Erzsébet; Wojnárovits, László

Hydroxyl radical-induced degradation of fenuron in pulse and gamma radiolysis: kinetics and product analysis

2014

Kovács, Krisztina | Mile, Viktoria | Csay, Tamás | Takács, Erzsébet | Wojnárovits, László

Radiolytic reactions of phenylureas were studied in detail with fenuron model compound in dilute aqueous solutions using pulse radiolysis for detection of the intermediates, gamma radiolysis with UV–Vis and HPLC-MS techniques for analysis of the final products. The kinetics of oxidation was followed by COD, TOC and toxicity measurements. During radiolysis of aerated solutions hydroxyl radical (•OH), eₐq⁻, H•and O₂•⁻/HO₂•reactive intermediates are produced, the degradation of solute takes place practically entirely through•OH reactions. Therefore, the product distribution is similar to the distributions reported in other advanced oxidation processes with•OH as main reactant.•OH mainly reacts with the aromatic ring, forming cyclohexadienyl radical as an intermediate. This radical in pulse radiolysis has a wide absorption band in the 310–390 nm wavelength range with a maximum at 350 nm. Cyclohexadienyl radical reacts with dissolved O₂with a rate coefficient of ∼4 × 10⁸ mol⁻¹ dm³s⁻¹forming peroxy radical. The latter may eliminate HO₂•giving phenols or undergoes fragmentation. The one-electron oxidant•OH on average induces more than two-electron oxidations. The toxicity first increases with absorbed dose, then decreases. This increase is partly due to phenols formed during the first degradation period.

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