Importance of Chain Length in Propagation Reaction on •OH Formation during Ozonation of Wastewater Effluent.

During the ozonation of wastewater, hydroxyl radicals (•OH) induced by the reactions of ozone (O3) with effluent organic matters (EfOMs) play an essential role in degrading ozone-refractory micropollutants. The •OH yield provides the absolute •OH formation during ozonation. However, the conventional "tert-Butanol (t-BuOH) assay" cannot accurately determine the •OH yield since the propagation reactions are inhibited, and there have been few studies on •OH production induced by EfOM fractions during ozonation. Alternatively, a "competitive method", which added trace amounts of the •OH probe compound to compete with the water matrix and took initiation reactions and propagation reactions into account, was used to determine the actual •OH yields (Φ) compared with that obtained by the "t-BuOH assay" (φ). The Φ were significantly higher than φ, indicating that the propagation reactions played important roles in •OH formation. The chain propagation reactions facilitation of EfOMs and fractions can be expressed by the chain length (n). The study found significant differences in Φ for EfOMs and fractions, precisely because they have different n. The actual •OH yield can be calculated by n and φ as Φ = φ (1 + n)/(nφ + 1), which can be used to accurately predict the removal of micropollutants during ozonation of wastewater.

Dissolved black carbon enhanced the aquatic photo-transformation of chlortetracycline via triplet excited-state species: The role of chemical composition.

Dissolved black carbon (DBC), widely distributed in the aquatic environments, can accelerate sunlight-driven photo-transformation of micropollutants, however the photosensitization mechanisms are not clear. Herein, the DBC was extracted from bamboo biochar and fractionated by molecular weight (i.e. <10 k, <3 k, and <1 k Da). The effects of DBC on chlortetracycline (CTC) photolysis behaviors, and the role of chemical composition (i.e., molecular weight and chemical structure) in DBC-mediated photo-transformation were investigated. The results showed that DBC could accelerate CTC photodegradation significantly. At low DBC concentrations (<6.0 mg C/L), the photodegradation rate constant of CTC increased from 0.0299 to 0.0416 min-1 with the increasing DBC concentration. Via quenching experiment, the triplet excited-state of DBC was identified as the dominant reactive intermediate with >90% contribution to total CTC photodegradation. In addition, it was found that the photosensitive efficiency of DBC increased as the molecular weight decreased, and the stronger photosensitization ability exhibited in DBC with low-molecular weight was potentially attributed to its higher content of carbonyl compounds. The observed photosensitive efficiency of DBC sharply decreased after reduction by NaBH4, further confirming the key role of carbonyl compounds in the photosensitization process. Moreover, based on the result of photoproducts, the amidogen in CTC was verified to be susceptible to react with 3DBC*.

Chlorella vulgaris enhance the photodegradation of chlortetracycline in aqueous solution via extracellular organic matters (EOMs): Role of triplet state EOMs.

Algae, which are ubiquitous in surface waters (e.g., lakes, ponds, wetlands) may play an important role in sunlight-driven transformation of compounds. This study is to investigate the role of algae (Chlorella Vulgaris) in chlortetracycline (CTC) photolysis and explore the photosensitive mechanism. The algae were found to significantly accelerate the photodegradation rate of CTC and extracellular organic matters (EOMs) were confirmed to be the major active substances. Triplet state EOMs (3EOMs*) were verified to be the dominant reactive species with 93% contribution to the indirect photodegradation rate of CTC, while ·OH and 1O2 contributed minor (7%). The steady-state concentration of 3EOMs* was determined by probe compounds (2,4,6-trimethylphenol) to be 3.50 × 10-14-1.88 × 10-13 M with the increase of EOMs from 2.0 to 8.0 mg L-1. The rate constant for reaction of 3EOMs* with CTC was calculated to be 3.17 × 109 M-1s-1. 3EOMs* were found to react with CTC mainly via electron transfer, on basis of susceptible reaction of 3EOMs* with the hydroxyl and amidogen groups in CTC. In addition, the energy transfer of 3EOMs* to CTC was possible according to the higher energy of 3EOMs* than that of triplet CTC.