Diethyl phthalate (DEP), as a kind of universally used plasticizer, has aroused considerable public concern owing to its wide detection, environmental stability, and potential health risks. In this work, the highly efficient removal of DEP by ferrate (VI) (Fe(VI)) was systematically explored in soil environment. The effects of the oxidant dosages, soil types, as well as the presence of coexisting cations and anions in tested soil on DEP removal were evaluated. When the dosage of Fe(VI) was 20 mM, complete removal of DEP (50 μg/g) was achieved in the tested soil after 2 min of reaction. Furthermore, the removal rate of DEP was closely related to the soil types, and the degradation rates were decreased obviously in red soil (RS), black soil (BS) and paddy soil (PS), probably due to the acidic condition and high content of organic matters. Moreover, the presence of Ca2+, Mg2+ and Al3+ in soil can inhibit the removal of DEP by Fe(VI), while SO42- has an slightly promotion effect. Six oxidation intermediates were detected in the reaction process of DEP, product analysis revealed that the transformation of DEP was mainly through two pathways, including hydrolysis and hydroxylation reactions, which were probably mediated by oxygen atom transfer process of Fe(VI). Based on the frontier electron density theory calculation, two ester groups of DEP were prone to be attacked by Fe(VI), and the hydroxyl addition tended to occur at the para-position of one of the ester groups on the benzene ring. This study provides a novel approach for phthalate esters removal from soil using Fe(VI) oxidation and shows new insights into the oxidation mechanisms.
Keywords: Diethyl phthalate; Ferrate (VI); Frontier electron density theory; Intermediates; Soil treatment.
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