Environmentally persistent free radicals (EPFRs) are occasionally detected in Superfund sites but the formation of EPFRs induced by polycyclic aromatic hydrocarbons (PAHs) is not well understood. In the present work, the formation of EPFRs on anthracene-contaminated clay minerals was quantitatively monitored via electron paramagnetic resonance (EPR) spectroscopy, and surface/interface-related environmental influential factors were systematically explored. The obtained results suggest that EPFRs are more readily formed on anthracene-contaminated Fe(III)-montmorillonite than in other tested systems. Depending on the reaction condition, more than one type of organic radicals including anthracene-based radical cations with g-factors of 2.0028-2.0030 and oxygenic carbon-centered radicals featured by g-factors of 2.0032-2.0038 were identified. The formed EPFRs are stabilized by their interaction with interlayer surfaces, and such surface-bound EPFRs exhibit slow decay with 1/e-lifetime of 38.46 days. Transformation pathway and possible mechanism are proposed on the basis of experimental results and quantum mechanical simulations. Overall, the formation of EPFRs involves single-electron-transfer from anthracene to Fe(III) initially, followed by H2O addition on formed aromatic radical cation. Because of their potential exposure in soil and atmosphere, such clay surface-associated EPFRs might induce more serious toxicity than PAHs and exerts significant impacts on human health.

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A facile hydrothermal approach has been developed to prepare defective TiO2−x nanocrystals using Ti(III)-salt as a precursor and L-ascorbic acid as reductant and structure direction agent. The prepared TiO2−x nanocrystals are composed of a highly crystallized TiO2 core and a disordered TiO2−x outer layer, possessing high surface area, controlled oxygen vacancy concentration and tunable bandgap via simply adjusting the amount of added L-ascorbic acid. The defective TiO2−x shows high photocatalytic efficiency in methylene blue and phenol degradation as well as in hydrogen evolution under visible light, underlining the significance of the present strategy for structural and bandgap manipulation in TiO2-based photocatalysis.

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