Simultaneous degradation and separation of antibiotics in sewage effluent by photocatalytic nanofiltration membrane in a continuous dynamic process.

Bifunctional photocatalytic nanofiltration (PNF) membrane is increasingly concerned in practical micro-polluted water purification, but there are still several bottlenecks that inhibit its practicality. In this context, the feasibility of a novel metal-free and visible light-responsive surface-anchored PNF membrane for simultaneously removing target antibiotics in real sewage effluent in a continuous dynamic process was explored. The results showed that the optimal PNF-4 membrane was expectedly consisted of an inside tight sub-nanopore structured separation layer and an outside thinner, smoother, super hydrophilic mesoporous degradation layer, respectively. Consequently, the activated PNF-4 membrane could synergistically reduce trimethoprim and sulfamethoxazole concentrations to below two orders of magnitude, accompanying with almost constant high water permeability, suggesting that the hydrophilic modification of the mesoporous degradation layer basically offsets its inherent hydraulic resistance. Also, after repeating the fouling-physical rinsing process three times lasted for 78 h, only sporadic adherent contaminants remained onto the top surface, together with the minimal total and irreversible fouling ratios (as low as 7.2% and 1.2%, respectively), strongly demonstrated that PNF-4 membrane displayed good self-cleaning performance. Undoubtedly, this will significantly reduce its potential cleaning frequency and maintenance cost in long-term operation. Meanwhile, the acute and chronic biotoxicities of its permeate to Virbrio qinghaiensis sp. -67 were also reduced sharply to 2.22% and 0.45%, respectively. All of these evidences suggest that the dual functions of PNF-4 membrane are synergetic in an uninterrupted permeating process. It will provide useful insights for continuously enhancing the practicality and effectiveness of PNF membrane in actual micro-polluted water purification scenarios.

Adsorption and fouling behaviors of customized nanocomposite membrane to trace pharmaceutically active compounds under multiple influent matrices.

Rare information is available on fouling behavior of customized nanofiltration (NF) membrane evoked by pharmaceutically active compounds (PhACs) under real multiple influent matrices pretreated by ultrafiltration module beforehand. To this end, a novel tight NF membrane with excellent perm-selectivity and antiadhesion was fabricated and used to assess its separation performance/mechanism and fouling behavior to a broad range of small molecular PhACs in the context. The adsorption ratio results revealed that the affinities between five selected PhACs and the customized nanocomposite membrane surface were all much weaker (below 5.5%) than the solute-solute interacting forces (between 23.6 and 83.2%), whether for natural or synthetic complex micropollutants. The predominant membrane fouling could be interpreted by the incomplete blocking model in the permeation of both influent conditions. For neat nanocomposite membrane, the order of critical factors important on separation mechanism was electrostatic effect, adsorption and steric hindrance. The fouling layer seemed to act as a secondary separating layer for those negatively charged or hydrophilic PhACs, but showed the cake enhanced concentration polarization effect for the neutral and hydrophobic ones. This study provides valuable insights for defining PhACs fate and NF membrane fouling behavior to fit increasingly stringent criteria for wastewater treatment.

Hydrophobic deep eutectic solvents as extractants for the determination of bisphenols from food-contacted plastics by high performance liquid chromatography with fluorescence detection.

As a new kind of green solvents for potential replacement of traditional volatile organic compounds, deep eutectic solvents (DESs) have been attracting more and more attention in various applications. In this work, three types of hydrophobic DESs were synthesized by simple mixing of trioctylmethyl ammonium chloride (used as hydrogen bond acceptor) with decanoic acid, ketoprofen and gemfibrozil (hydrogen bond donors), respectively, at different molar ratios. In order to evaluate the solvent characteristics of these DESs, some of the physical properties such as melting point, density, viscosity, and water contact angle were determined. Then, these hydrophobic DESs were used for the vortex-assisted liquid-liquid microextraction of bisphenol-type contaminants in water, followed by quantitative determination of bisphenols contents with high performance liquid chromatography (HPLC-FLD) coupled with fluorescence detection. For this purpose, four bisphenols, namely, 2, 2-bis(4-hydroxydiphenyl)propane (BPA), 2, 2-bis (4-hydroxyphenyl)butane (BPB), 4, 4'-(1-phenylethylidene)bisphenol (BPAP) and 4, 4'-cyclohexylidenebisphenol (BPZ) were selected as model contaminants. It was found that the enrichment factors of the proposed method were in the range from 97 to 112, depending on the structure of the analytes. Under optimal experimental conditions, the linearity ranges of the method varied from 0.3 to 700 µg L-1 with linear correlation coefficients (R2) higher than 0.996. The limit of detections (LODs) and limit of quantifications (LOQs) were in the range of 0.3-0.5 µg L-1 and 0.06-0.08 µg L-1, respectively. Furthermore, the developed method was successfully used in the extraction and determination of four bisphenols from food-contacted plastic samples.

New low viscous hydrophobic deep eutectic solvents in vortex-assisted liquid-liquid microextraction for the determination of phthalate esters from food-contacted plastics.

In this work, a novel class of eight low viscosity hydrophobic deep eutectic solvents (DESs) has been designed and prepared from two kinds of quaternary ammonium salts and six kinds of water-insoluble fatty alcohols/acids. Several physical properties of these DESs, such as melting point, density and viscosity, have been determined to investigate their adaptability as solvents. Then, such DESs are used as extraction solvents in a vortex-assisted liquid-liquid microextraction for the extraction and preconcentration of phthalate esters (PEs) from water samples, and the content of PEs from food-contacted plastics is then determined by using gas chromatography. It is found that the analytic method developed in this work exhibits wide linear range of 5-1000 µg L-1, and the limit of detections for target analytes is as low as 1 µg L-1. Finally, the proposed method has been successfully used for the determination of PEs from food-contacted plastics.