Qing Zhou

Quaternized magnetic microspheres for the efficient removal of reactive dyes

In this paper, a novel quaternized magnetic resin, NDMP, was prepared and characterized. Two reactive dyes (RDs), Orange G (OG) and red RWO, were used as a small-molecular RD and large-molecular RD, respectively, to investigate their adsorption on NDMP. A common quaternized magnetic resin, MIEX, was selected for comparison. The adsorption kinetics of OG onto both resins and the adsorption kinetics of RWO onto NDMP followed pseudo-second-order kinetics, whereas the adsorption of RWO onto MIEX was better fitted by pseudo-first-order kinetics. The experimental data illustrated that the equilibrium adsorption amount of both RDs onto NDMP (1.9 mmol OG/g, 0.70 mmol RWO/g) was twice as large as that on MIEX (1.0 mmol OG/g, 0.35 mmol RWO/g). The Langmuir equation and the Freundlich model fit the isotherm data for OG and RWO adsorption, respectively. The adsorption of OG on the NDMP and MIEX resins declined in the presence of NaCl or Na₂SO₄. The effects of the salts on the adsorption of RWO were different. The recyclability of NDMP and MIEX were also evaluated. This work provides a reusable efficient adsorbent for the removal of RDs.

HPLC/HPSEC-FLD with multi-excitation/emission scan for EEM interpretation and dissolved organic matter analysis.

The need to track and characterize dissolved organic matter (DOM) has made fluorescence excitation-emission matrix (EEM) spectroscopy extensively used. In this work, reverse phase high-performance liquid chromatography (RP-HPLC) and high-performance size exclusion chromatography (HPSEC) with fluorescence detector (FLD) were used for EEM interpretation and DOM analysis. Given that fluorescence detectors can scan with multi-excitation or multi-emission mode, HPLC-FLD with multi-excitation scan directly verified the prevalence of multi-peak fluorophores in EEM, which provides a corrective insight for the current fluorescence regional integration (FRI) methods; whereas HPLC-FLD with multi-emission scan provided more informative fluorescence fingerprints for identification of DOM species, which is a chromatographic surrogate for determining the proper number of PARAFAC components. Besides providing a deep insight for the current EEM interpretation, the HPLC/HPSEC-FLD results also directly related physiochemical properties to DOM species, including polarity and molecular weight (MW) distribution, which is helpful for further characterization their behavior in water and wastewater treatment process. A chromatography technique with multi-excitation and multi-emission fluorescence scan can be an informative method for EEM interpretation and DOM identification and characterization.

Enhanced adsorption and antifouling performance of anion-exchange resin by the effect of incorporated Fe3O4 for removing humic acid

The application of anion-exchange resins (AERs) is limited by fouling, which increases the fresh resin dosage, regeneration frequency, and amount of regeneration effluent. In this study, five AERs with different Fe3O4 amounts was prepared by increasing the amount of Fe3O4 added to 100 g of monomer mixture for suspension polymerization from 0 g to 40 g. Results showed considerably improved pore volume and hydrophilicity of the resin with increased Fe3O4 content, leading to significantly enhanced adsorption and desorption of humic acid. A method of developing novel resins with enhanced adsorption and antifouling abilities by incorporating Fe3O4 was then proposed. The adsorbent structure resulting from the incorporated inorganic particles was found to be important in determining the adsorption behavior of a hybrid adsorbent.

A magnetic sorbent for the efficient and rapid extraction of organic micropollutants from large-volume environmental water samples

A magnetic solid-phase extraction (MSPE) method based on a novel magnetic sorbent was proposed for the extraction of target compounds from large-volume water samples. First, magnetic hypercrosslinked microspheres (NAND-1) were prepared via membrane emulsification-suspension polymerization and post crosslinking reaction. To ensure that the Fe3O4 nanoparticles could completely pass through the membrane without blocking the pores, oleic acid was used to modify the Fe3O4 nanoparticles, which enhanced lipophilicity and monodispersity of the magnetite nanoparticles. The obtained NAND-1 microspheres exhibited super paramagnetic characteristics and excellent magnetic responsiveness with a saturation magnetization of 2.53 emu/g. In addition, a uniform particle size (~8 μm) and a large average surface area (1303.59 m(2)/g) were also observed, which were both beneficial for the extraction of the target compounds. Thus, NAND-1 has the potential to simultaneously exhibit good extraction efficiencies toward different types of organic micropollutants (OMPs), including triazines, carbamazepine and diethyl phthalate. The conditions of the MSPE based on NAND-1 were optimized by single factor and orthogonal design experiments. This MSPE method needed only a small amount of sorbent (50mg/L) for the extraction of OMPs from a large-volume aquatic sample (5L) and reached equilibrium in a short amount of time (30 min). Moreover, the solution volume, the pH, and the salinity had insignificant influences on the extraction of the eight target OMPs. Under the optimum conditions, the recoveries of the eight OMPs calculated by analyzing the spiked samples were from 91.7% to 99.4%. The NAND-1 could be recycled ten times and still achieve recoveries of the eight OMPs higher than 86%. The limits of detection of the eight OMPs ranged from 1.76 to 27.56 ng/L, and the limits of quantification were from 5.71 to 92.05 ng/L. These results indicated that the proposed method, based on the use of NAND-1 as a magnetic sorbent, has the advantages of convenience and high efficiency and can be successfully applied to analyze the OMPs in real water samples.

Fouling of anion exchange resin by fluorescence analysis in advanced treatment of municipal wastewaters

The application of anion exchange resins (AERs) has been limited by the critical problem of resin fouling, which increases the volume of the desorption concentrate and decreases treatment efficiency. To date, resin fouling has not been well studied and is poorly understood compared to membrane fouling. To reflect the resin fouling level, a resin fouling index (RFI) was established in this work according to the decrease of DOC removal after regeneration of the resin for the advanced treatment of municipal wastewater. Comparing the linear fitting results between the RFI and the fluorescence intensity indicated that the resin fouling was related to the protein-like substances with fluorescence peak T in the region of excitation wavelength <250xa0nm and emission wavelength <380xa0nm. Using their fluorescent characteristics as a label, the protein-like substances causing the fouling were further identified as hydrophilic components with molecular weights greater than 6500xa0Da.

Preparation of a novel anion exchange group modified hyper-crosslinked resin for the effective adsorption of both tetracycline and humic acid

A novel hyper-crosslinked resin (MENQ) modified with an anion exchange group was prepared using divinylbenzene (DVB) and methyl acrylate (MA) as comonomers via four steps: suspension polymerization, post-crosslinking, ammonolysis and alkylation reactions. The obtained resin had both a high specific surface area (793.34 m2·g−1) and a large exchange capacity (strong base anion exchange capacity, SEC: 0.74 mmol·g−1, weak base anion exchange capacity, WEC: 0.45 mmol·g−1). XAD-4 was selected as an adsorbent for comparison to investigate the adsorption behavior of tetracycline (TC) and humic acid (HA) onto the adsorbents. The results revealed that MENQ could effectively remove both TC and HA. The adsorption capacity of XAD-4 for TC was similar to that of MENQ, but XAD-4 exhibited poor performance for the adsorption of HA. The adsorption isotherms of TC and HA were well-fitted with the Freundlich model, which indicated the existence of heterogeneous adsorption through cation-π bonding and π-π interactions. The optimal solution condition for the adsorption of TC was at a pH of 5–6, whereas the adsorption of HA was enhanced with increasing pH of the solution.

Preparation of Uniform Hypercrosslinked Microspheres with Large Specific Surface Area

The membrane emulsification-suspension polymerization (MESP) method was used to synthesize hypercrosslinked microspheres with a narrow size distribution. The resulting polymers possessed large specific surface area (over 1300 m2/g) and their particle size was controllable. The particles were more hydrophilic when using nitrobenzene as solvent instead of 1, 2-dichloroethane in the postcrosslinking process.

New Hypercrosslinked Polymer Adsorbents for Solid Phase Extraction of Polar Compounds

Membrane emulsification-suspension polymerization method was introduced to prepare the monodisperse hypercrosslinked adsorbents ZQ-1 and ZQ-2 which can be used in solid phase extraction (SPE). Compared with the commercially available adsorbent LichrolutEN, ZQ-1 exhibits obvious superiority for five conventional polar analytes owing to its large specific surface area, hydrophilic groups and small particle size.