Simultaneous Degradation, Dehalogenation, and Detoxification of Halogenated Antibiotics by Carbon Dioxide Radical Anions

Despite the extensive application of advanced oxidation processes(AOPs)in water treatment,the efficiency of AOPs in eliminating various emerging contaminants such as halogenated antibiotics is constrained by a number of factors.Halogen moieties exhibit strong resistance to oxidative radicals,affecting the dehalogenation and detoxification efficiencies.To address these limitations of AOPs,advanced reduction processes(ARPs)have been proposed.Herein,a novel nucleophilic reductant—namely,the carbon dioxide radical anion(CO_(2)^(·-))—is introduced for the simultaneous degradation,dehalogenation,and detoxification of florfenicol(FF),a typical halogenated antibiotic.The results demonstrate that FF is completely eliminated by CO_(2)^(·-),with approximately 100%of Cland 46%of Freleased after 120 min of treatment.Simultaneous detoxification is observed,which exhibits a linear response to the release of free inorganic halogen ions(R^(2)=0.97,p<0.01).The formation of halogen-free products is the primary reason for the superior detoxification performance of this method,in comparison with conventional hydroxyl-radical-based AOPs.Products identification and density functional theory(DFT)calculations reveal the underlying dehalogenation mechanism,in which the chlorine moiety of FF is more susceptible than other moieties to nucleophilic attack by CO_(2)^(·-).Moreover,CO_(2)^(·-)-based ARPs exhibit superior dehalogenation efficiencies(>75%)in degrading a series of halogenated antibiotics,including chloramphenicol(CAP),thiamphenicol(THA),diclofenac(DLF),triclosan(TCS),and ciprofloxacin(CIP).The system shows high tolerance to the pH of the solution and the presence of natural water constituents,and demonstrates an excellent degradation performance in actual groundwater,indicating the strong application potential of CO_(2)^(·-)-based ARPs in real life.Overall,this study elucidates the feasibility of CO_(2)^(·-)for the simultaneous degradation,dehalogenation,and detoxification of halogenated antibiotics and provides a promising method for their regulation during water or wastewater treatment.

Removal of gaseous acetic acid using ionic liquid [EMIM][BF_4]

This work proposed to use the ionic liquid [EMIM][BF_4] as absorbent for the absorption of gaseous acetic acid. The feasibility of this technology was investigated from molecular level to industrial scale. The acetic acid absorption experiment was carried out using [EMIM][BF_4],and the removal ratio of acetic acid in the gas product can achieve 88.6% at 20C under atmospheric pressure at the laboratory scale. Based on the experimental results, a reliable strict equilibrium phase model embedding the parameters of the UNIFAC model was established. On this basis, the conceptual process design and optimization of acetic acid removal by [EMIM][BF_4] at an industrial scale was done, and the most suitable design and operation parameters were obtained. For a further step, the binding energy between [EMIM][BF_4] and acetic acid was calculated to give some insights into the separation mechanism, and the results indicate that the interaction between acetic acid and IL is much stronger than that between nitrogen and IL. Moreover, hydrogen bond can be formed between the cation-acetic acid as well as the anion-acetic acid.