Chengjun Wang

Analysis of phenolic pollutants in human samples by high performance capillary electrophoresis based on pretreatment of ultrasound-assisted emulsification microextraction and solidification of floating organic droplet.

A novel, simple and rapid method, termed ultrasound-assisted emulsification microextraction and solidification of floating organic droplet (UAEM-SFO) coupled to high performance capillary electrophoresis (HPCE), was developed for preconcentration and analysis of five phenolic compounds (PCs) in human urine and blood samples. The proposed method is based on microextraction of target analytes in less-toxic organic solvent under assistance of ultrasound. A micro-droplet of less-toxic organic solvent floating on the surface of liquid samples in a sealed vial can be dispersed into sample solutions under the ultrasound frequency, solidified under ice bath, collected with a medicine spatula, molten at ambient temperature, and finally subjected to HPCE analysis. The parameters of UAEM-SFO procedure including type and volume of extraction solvent, extraction temperature, time of ultrasound-assisted extraction and centrifugation, sample pH, and ionic strength were optimized. The influence parameters on HPCE resolution such as pH, concentration of running buffer, applied voltage and injection time were also investigated. This method requires only 40 μL of 2-dodecanol extraction solvent and 8 min of pretreatment time. The enrichment factors of analytes were in the range of 114-172 and extraction recoveries (69-86%) were obtained. Good linearity was achieved for five analytes in the range of 0.05-100 μg L⁻¹ and the correlation coefficients ranged from 0.9934 to 0.9999. The limits of detection were 0.01 μg L⁻¹ for triclosan (TCS) and biophenol A (BPA), and 0.02 μg L⁻¹ for pentachlorophenol (PCP), 2,4-dichlorophenol (2,4-DCP) and 4-nonylphenol (4-NP) in urine samples, and 0.02 μg L⁻¹ for TCS and BPA, 0.04 μg L⁻¹ for PCP, 2,4-DCP and 4-NP in blood samples. The developed UAEM-SFO-HPCE method has a great potential in routine residual analysis of trace PCs in biological samples.

Ionic liquids dispersive liquid-liquid microextraction and high-performance liquid chromatographic determination of irbesartan and valsartan in human urine.

An environmentally friendly ionic liquids dispersive liquid-liquid microextraction (IL-DLLME) method coupled with high-performance liquid chromatography (HPLC) for the determination of antihypertensive drugs irbesartan and valsartan in human urine samples was developed. The HPLC separations were accomplished in less than 10 min using a reversed-phase C(18) column (250 × 4.60 mm i.d., 5 µm) with a mobile phase containing 0.3 % formic acid solution and methanol (v/v, 3:7; flow rate, 1.0 mL/min). UV absorption responses at 236 nm were linear over a wide concentration range from 50 µg/mL to the detection limits of 3.3 µg/L for valsartan and 1.5 µg/L for irbesartan. The effective parameters on IL-DLLME, such as ionic liquid types and their amounts, disperser solvent types and their volume, pH of the sample and extraction time were studied and optimized. The developed IL-DLLME-HPLC was successfully applied for evaluation of the urine irbesartan and valsartan profile following oral capsules administration.

Determination of free and total phthalates in commercial whole milk products in different packaging materials by gas chromatography-mass spectrometry

We developed a method for extraction and determination of free and total phthalate esters in commercial whole milk products. The free phthalates in milk samples were extracted with ethyl acetate after general pretreatment procedures including protein precipitation, centrifugation, and filtration. The bound phthalates in samples were first desorbed with the aid of ultrasound irradiation before extraction of total phthalates. The separation and determination of phthalates in extracts was performed by gas chromatography coupled with mass spectrometric detection. The detection limits were in the range of 0.09 to 0.36ng/g and the average recovery between 79.1 and 110.3%. The developed methods were applied to extract and determine phthalates in commercial whole milk products with different packaging materials, including plastic, glass, and metal. All samples contained several phthalates, including diethyl, diisobutyl, and bis(2-ethylhexyl) phthalates at concentrations between 2.60 and 156.4ng/g. The identified phthalates occurred in both free and bound forms. The amounts of phthalates in milk samples packaged in glass and metal containers were much lower than those in plastic containers. Plastic packaging materials are a possible source of phthalate contamination in commercial whole milk products, and a considerable portion of bleached phthalates from packaging can be adsorbed on proteins and other solid components of milk.

Modification to degradation of hexazinone in forest soils amended with sewage sludge

Influences of one sewage sludge on degradation of hexazinone and formation of its major metabolites were investigated in four forest soils (A, B, C and D), collected in Zhejiang Province, China. In non-amended forest soils, the degradation half-life of hexazinone was 21.4, 30.4, 19.4 and 32.8 days in forest soil A, B, C and D, respectively. Degradation could start in soil A and C without lag period because the two soils had been contaminated by this herbicide for a long time, possibly leading to completion of acclimation period of hexazinone-degrading bacteria. In forest soils amended with sewage sludge, the degradation rate constant increased by 17.3% in soil A, 48.2% in soil B, 8.1% in soil C and 51.6% in soil D, respectively. The higher degradation rates (soil A and C) in non-amended soils accord with the lower rate increase in sewage sludge-amended soils. Under non-sterile conditions, biological mechanism accounted for 51.8-62.4% of hexazinone degradation in four soils. Under sterile conditions, the four soils had the similar chemical degradation capacity for hexazinone. In non-amended soil B, only one metabolite (B) was detected, while two metabolites (B and C) were found in sewage sludge-amended soil B. Similarly situated in agricultural soils, N-demethylation at 6-position of triazine ring, hydroxylation at the 4-positon of cyclohexyl group, and removal of the dimethylamino group with formation of a carbonyl group at 6-position of triazine ring appear to be the principal mechanism involved in hexazinone degradation in sewage sludge-amended forest soils. These data will improve understanding of the actual pollution risk as a result of forest soil fertilization with sewage sludge.

Dispersive solid-phase microextraction with graphene oxide based molecularly imprinted polymers for determining bis(2-ethylhexyl) phthalate in environmental water

A novel graphene oxide-molecularly imprinted polymers (GO-MIPs) was prepared and applied for selective extraction and preconcentration of bis(2-ethylhexyl) phthalate (DEHP) in environmental water samples by using the dispersive solid-phase microextraction (DSPME) method. The GO-MIPs was synthesized via precipitation polymerization using GO, DEHP, methacrylic acid, and ethylene dimethacrylate as supporting materials, template molecules, functional monomer, and cross-linker, respectively. The prepared GO-MIPs were characterized by scanning electron microscope and Fourier transform infrared spectroscopy. The GO-MIPs-DSPME conditions including type and volume of elution solvents, adsorbents amount, initial concentration of DEHP, pH and ionic strength of water samples were investigated. Under optimized conditions, the DEHP was selectively and effectively extracted in real water samples and enrichment factors of over 100-fold were achieved. Good linearity was obtained with correlation coefficients (R2) over 0.999 and the detection limit (S/N=3) was 0.92ngmL-1. The average recoveries of the spiked samples at three concentration levels of DEHP ranged from 82% to 92% with the relative standard deviations less than 6.7%. The results indicated that the proposed GO-MIPs-DSPME extraction protocol combined with HPLC-UV determination could be applied for selective and sensitive analysis of trace DEHP phthalate in environmental water samples.

Halloysite-nanotubes supported FeNi alloy nanoparticles for catalytic decomposition of toxic phosphine gas into yellow phosphorus and hydrogen

The FeNi alloy nanoparticles (FeNi and BFeNi) supported on natural halloysite nanotubes (HNTs) were prepared for catalytic decomposition of toxic phosphine (PH₃) to yellow phosphorus and hydrogen. The Fourier transform infrared spectroscopy, X-ray diffraction, inductively coupled plasma, scanning electron microscope, and hydrogen temperature-programmed reduction tests were carried out to characterize the physicochemical properties of HNTs and the prepared nano-catalysts. Nearly 100% PH₃ was decomposed into yellow phosphorus and hydrogen at 420 °C with prepared FeNi/HNTs catalysts. Metallic Ni and Fe₃O₄ could be the catalytic active sites in FeNi/HNTs for PH₃ decomposition under the low temperature. The boron (B) additives decrease the catalytic activity of FeNi/HNTs for PH₃ decomposition due to the formation of the spinal NiFe₂O₄ and Fe₂B which replace the active Fe₃O₄ and metallic Ni in catalysts. The developed FeNi/HNTs are low-cost and effective catalysts for air-pollution control and recycle of the hazardous waste PH₃ gas in industry.

Advances on transition metal oxides catalysts for formaldehyde oxidation: A review

ABSTRACT This article highlights recent advances in the development of transition metal-based catalysts for formaldehyde oxidation, particularly the enhancement of their catalytic activity for low-temperature oxidation. Various factors that enhance low-temperature activity are reviewed, such as morphology and tunnel structures, synthesis methods, specific surface area, amount and type of active surface oxygen species, oxidation state, and density of active sites are discussed. In addition, catalyst immobilization for practical air purification, reaction mechanism of formaldehyde oxidation, and the reaction parameters affecting the overall efficiency of the reaction are also reviewed.

Extraction of natural estrogens in environmental waters by dispersive multiwalled carbon nanotube-based agitation-assisted adsorption and ultrasound-assisted desorption

A dispersive multiwalled carbon nanotube (MWCNT) based agitation-assisted adsorption and ultrasound-assisted desorption method has been developed for extracting natural estrogenic steroids in environmental waters prior to high performance liquid chromatography-diode array detection (HPLC-DAD) analysis. With the aid of agitation, the trace estrogens in bulk aqueous solution were adsorbed onto milligrams of dispersive MWCNTs. After filtration, the estrogens enriched on MWCNT nanoparticles were quickly desorbed into milliliters of organic solvent in an ultrasonic bath. Finally, the analytes in the organic solvent were directly determined by HPLC-DAD. The stability examination of estrogens under the tested ultrasonic irradiation was performed and the results indicated that the estrogens were stable during the extraction process. Several parameters that could influence the extraction efficiency, such as type and volume of desorption solvent, consumed amount of MWCNTs, pH and ionic strength of sample solution, agitation-assisted adsorption and ultrasound-assisted desorption time, were examined. Under the optimized conditions, the recoveries for three analytes in spiked samples were over 82%. The detection limits were 0.076 ng mL−1 for estrone, 0.049 ng mL−1 for 17β-estradiol, and 0.057 ng mL−1 for estriol, respectively, while the relative standard deviations were less than 9% (at the 20 ng mL−1 estrogen level for 10 runs).

Effects of imidazolium room temperature ionic liquids on the fluorescent properties of norfloxacin

The effects of 12 imidazolium room temperature ionic liquids (RTILs), including [C(n)mim]BF4, [C(n)mim]PF6, and [C(n)mim]Br (n = 4, 6, 8, 10), on the fluorescent properties of norfloxacin were examined. The fluorescence intensity of norfloxacin at 0.1 mg/L in methanol significantly increased with the addition of [C(n)mim]BF4 and [C(n)mim]PF6 into the solvent at 0.1-15.0%. The sensitizing effect may result from the higher viscosity of the RTILs-methanol mixture solvent than that of the methanol itself. However, the quenching effect on fluorescence of norfloxacin was observed in [C(n)mim]Br-methanol solvent. The fluorescence intensities of norfloxacin decreased with an increase in the alkyl chain length of the alkyl substituents of the imidazolium ring of RTILs. The main interaction between the RTILs and norfloxacin is not by hydrogen bonding. The fact, that some RTILs can significantly sensitize fluorescence of norfloxacin, indicates that RTILs could be a group of promising solvents for development of sensitive spectrofluorimetric methods for determination of norfloxacin at ultra-trace levels in environmental samples.

Occurrence and photodegradation of methylmercury in surface water of Wen-Rui-Tang River network, Wenzhou, China

The spatial distribution and seasonal variations of methylmercury (MeHg) in Wen-Rui-Tang (WRT) River network were investigated by monitoring the MeHg concentrations in surface water samples collected from 30 sites across the river network over four seasons. Detection frequencies and concentrations of MeHg were generally higher in January, indicating that low sunlight irradiation, wind speed, and temperature conditions might enhance the persistence of MeHg in surface water. The MeHg levels varied with sampling locations, with the highest concentrations being observed in the industrial area especially around wastewater outfall, revealing that the mercury contamination in WRT River mainly comes from the industrial wastewater. Photodegradation of MeHg in WRT River surface water and the effects of natural constituents such as fulvic acid (FA), ferric ions (Fe3+), nitrate (NO3−), and dissolved oxygen on the MeHg photodegradation in aqueous solutions were studied under the simulated sunlight. The experimental data indicated that the indirect photodecomposition of MeHg occurred in WRT River surface water. Photodegradation of MeHg in FA solution was initiated by triplet 3FA* or MeHg-FA* via electron transfer interaction under light irradiations. The Fe3+ and NO3− can absorb light energy to produce ·OH and enhance the photochemical degradation of MeHg. The MeHg photodecompositions in FA, nitrate, and Fe3+ solutions were markedly accelerated after removing the dissolved oxygen.