Trace analysis of Pt (IV) metal ions in roadside soil and water samples by Fe3O4/graphene/polypyrrole nanocomposite as a solid-phase extraction sorbent followed by atomic absorption spectrometry

A novel Fe₃O₄/graphene/polypyrrole nanocomposite has been successfully synthesised via a simple chemical method and applied as a new magnetic solid-phase extraction (MSPE) sorbent for the separation and pre-concentration of trace amounts of Pt (IV) in environmental samples followed by flame atomic absorption spectrometric (FAAS) detection. The nanocomposite has been characterised by scanning electron microscopy (SEM), transmission electron microscopy (TEM) and Fourier transform infrared (FTIR) spectroscopy. Seven important parameters, affecting the extraction efficiency of Pt (IV), including pH, adsorption time, desorption solvent type and concentration, desorption time, elution volume and sample volume, were investigated. Under the optimised conditions, the calibration graph was linear in the range of 50–1500 μg L^?1 (R = 0.993). The detection limit and pre-concentration factor (PF) for Pt (IV) were found to be 16 μg L^?1 and 112.5, respectively. Under the optimised solid-phase extraction (SPE) conditions, the adsorption isotherm and the adsorption capacity of the nanocomposite for Pt (IV) were studied. Pt (IV) adsorption equilibrium data were fitted well to the Langmuir isotherm and the maximum adsorption capacity of the magnetic sorbent was calculated from the Langmuir isotherm model as 416.7 mg g^?1. The precision of the method was studied as intraday and interday variations. A relative standard deviation percentage (RSD%) value less than 3.0 indicates that the method is precise. Also, the accuracy of the method was tested by the analysis of the standard reference material (NIST SRM 2556) and by recovery measurements on spiked real samples. It was also shown that the optimised method was suitable for the analysis of trace amounts of Pt (IV) in roadside soil, tap water and wastewater samples.     

An on-line solid phase extraction-liquid chromatography tandem mass spectrometry method for the determination of perfluoroalkyl substances in the Antarctic ice core samples

An on-line solid phase extraction-high performance liquid chromatography-tandemmass spectrometry method for the analysis of perfluoroalkyl substances (PFASs) in water samples was developed. The optimal analytical conditions were obtained through the optimization of the extraction efficiency of online solid phase extraction column, sample loading rate and loading volume, and the concentration of ammonium acetate in mobile phase. Under the optimal condition, the analytical method displayed good linearity (r² > 0.99) for 12 PFASs (C5-C14 perfluoroalkyl carboxylic acids and C6/C8 perfluoroalkyl sulfonic acids) over a concentration range of 0.5-100 ng/L. The limits of quantitation for samples were between 0.025 ng/L and 0.5 ng/L and the relative standard deviations (RSD) of five consecutive analyses were less than 10% for 1 ng/L standard solution. Satisfactory results were obtained using this analytical method for the analysis of perfluoroalkyl substances in Antarctic ice core samples. The recoveries of all perfluoroalkyl substances were in a range of 73%-117% when the sampleswere spiked with standards at the concentrations of 2.5 ng/L and 25 ng/L.     

离子液体自聚集磁性多壁碳纳米管固相萃取环境水样中的磺胺类药物

将1-己基-3-甲基咪唑六氟磷酸([C6MIM] [PF6])离子液体自聚集于磁性多壁碳纳米管(Fe3O4@MWCNTs)表面,并将其作为磁性固相吸附剂,建立了同时测定环境水样中磺胺二甲嘧啶、磺胺对甲氧嘧啶、磺胺邻二甲氧嘧啶和磺胺二甲异噁唑4种磺胺类药物的涡旋辅助磁性固相萃取-高效液相色谱法.优化条件为:将20.0 mg [C6MIM] [PF6]包覆的Fe3 O4@MWCNTs分散于200 mL水样中,涡旋萃取15 min,磁性分离获取磁性吸附剂,3.5 mL 1.0％乙酸铵-甲醇溶液洗脱,洗脱液氮吹至干,300 μL甲醇溶解后待下一步高效液相色谱/二极管阵列检测器(HPLC-PDA)分析.4种磺胺类药物在0.375 ～ 75.0 μg/L范围内与峰面积呈良好的线性关系,其相关系数为0.9985 ～0.9996,检出限(S/N=3)为0.079 ～0.099 μg/L,3个加标浓度水平的回收率为80.60％ ～99.99％,日内、日间测定的相对标准偏差分别为1.3％ ～6.9％和1.2％～2.9％(n=3).结果表明,本方法简单方便,易于操作,适用于环境水样中痕量磺胺类药物的检测.     

基于愈创木酚荧光减量准确测定过氧化物酶活性的新方法

利用H2O2/过氧化物酶(POD)/愈创木酚(GA)反应体系的产物(470 nm)吸光度去定量POD活性是目前常用方法之一,但产物不稳定且对比色皿有吸附现象是该反应的主要缺点之一。为了解决此问题,本研究利用GA的荧光特性建立了一种能准确测定POD活性的方法。用辣根过氧化物酶( HRP)作为测试样品得到了以下优化条件：0.5 mmol/L GA,0.5 mmol/L H2O2,0.05 mol/L PBS缓冲液(pH 6.0),反应温度20℃,样品耗量20μL;本方法的线性范围为500~60000 U/L(r=0.9993),RSD≤2.4%(n=11),检出限为385 U/L。在优化条件下,用白萝卜提取液作为测试样品,用本方法((9714依132) U/L)与比色法((9926依352) U/L)和循环催化流动分析法((9608依456) U/L)进行了对比,结果表明,3种方法相互一致性很好。     

Preparation of a new Cu(II)-imprinted polymer and its application for the determination of trace copper in water samples by flame atomic absorption spectrometry

A new Cu(II)-imprinted polymer has been prepared for selective solid-phase extraction of Cu(II) prior to its determination by flame atomic absorption spectrometry. Two functional monomers, 4-(methacryloylamino)benzamide and 4-vinylpyridine, formed a complex with Cu(II) ion through coordination interactions. The self-assembled Cu(II)-monomer complex was copolymerised via bulk polymerisation method in the presence of ethyleneglycoldimethacrylate cross-linker. In order to remove Cu(II) ions, the resulting polymer was washed with 1.0 M HNO₃ and then with water until obtaining a neutral pH. The ion imprinted polymer was characterised by Fourier transform infrared. The experimental conditions were optimised for solid-phase extraction of Cu(II) using a column of ion-imprinted polymer (IIP). Quantitative retention was achieved between pH 5.0 and 7.0, whereas the maximum recovery for the non-imprinted polymer (NIP) was about 74% at pH 7.0. The IIP showed higher selectivity to Cu(II) in comparison to the NIP. The IIP also exhibited excellent selectivity for Cu(II) in the presence of other metal ions. The relative standard deviation and limit of detection (3s) of the method were 1.6% and 1.8 µg L^?1, respectively. The method was verified by analysis of two certified reference materials (CWW-TM-D and SRM 3280) and then applied to the determination of Cu(II) in seawater and lake water samples and haemodialysis concentrates.     

Pesticide residues analysis in honey using ethyl acetate extraction method: validation and pilot survey in real samples

This paper presents a cost-effective and validated multi residue confirmatory method for the determination of 167 chemically different pesticides and a survey study on Cyprus honey samples. This method uses ethyl acetate for the extraction of pesticides from honey and the determination is performed with liquid chromatography (LC) coupled to mass spectrometry (MS) operating in tandem mode (MS/MS) and with GC–ECD (gas chromatography with electron capture detector) analysis. The LC-MS/MS analytical system is especially important in the analysis of polar and non-volatile pesticides. For the validation of the method, blank honey samples were spiked with 146 pesticides (organophosphorous, carbamates, triazoles, amides, neonicodinoids, strobilurines, phenylureas, bendimidazoles and others) for the LC-MS/MS analysis at three levels: 0.01, 0.05 and 0.1 mg kg^?1 and with 21 pesticides for the GC-ECD analysis at two levels: 0.01 and 0.05 mg kg^?1for organochlorines and 0.05 and 0.2 mg kg^?1for the pyrethroids. As blank sample, a sample of honey which did not contain detectable levels of the analytes sought was used. The validation study was in accordance to the DG SANCO guidelines. The scope of validation included recovery, linearity, limits of quantification and precision. Linearity is demonstrated all along the range of concentration that was investigated with correlation coefficients ≥0.98. Recoveries of the majority of compounds were in the 70%–120% range and were characterised by precision lower or equal to 20%. The validated method was used for a survey of 36 samples of honey produced in different areas of Cyprus and this is the first work on Cypriot honey samples investigating a broad range of pesticides. Only coumaphos was detected at concentrations higher than 0.01 mg kg^?1 in the 58.6% of the honey samples analysed for Coumaphos. The results were evaluated in accordance to the provisions of the Commission Regulation (EU) No 37/2010 on pharmacologically active substances and their classification regarding maximum residue limits (MRLs) in foodstuffs of animal origin. The concentrations of coumaphos in all positive samples were at levels much lower than the MRL.     

Solid-phase extraction of Pb2+ ion from environmental samples onto L-AC-Ag-NP by flame atomic absorption spectrometry (FAAS)

The development of a solid-phase extraction (SPE) procedure for the pre-concentration of trace amounts of Pb²⁺ ion on 2-furan-2-yl-1-furan-2-ylmethyl-1H-benzoimidazole loaded on activated carbon modified with silver nanoparticles (L-AC-Ag-NP) was presented. The metal ion retained on the sorbent was quantitatively determined via complexation with the ligand. The complexed metal ion was efficiently eluted using 10 mL of 4 mol L^?1 sulphuric acid in 10 w/v% acetone. The influences of the analytical parameters, including pH, amounts of the ligand and the solid phase, eluent conditions and sample volume, on the recoveries of the metal ion were optimised. Using the optimised parameters, the linear response of the SPE method for Pb²⁺ ion were in the ranges of 0.2–160 µg L^?1, and the detection limit for Pb²⁺ ion was 0.034 µg L^?1. The proposed method exhibits a pre-concentration factor (PF) of 80 and an enhancement factor of 30 for Pb²⁺ ion. The presented results demonstrate the successful application of the proposed method for the determination of Pb²⁺ ion in some real samples with high recoveries (>93%) and reasonable relative standard deviation (RSD < 2%).     

Microwave-assisted micro-solid-phase extraction for analysis of tetracycline antibiotics in environmental samples

In this study, a novel solid-liquid-solid extraction approach, which was termed ‘microwave-assisted micro-solid-phase extraction’ (MAE-μ-SPE), was developed. Target analytes were extracted from the sample into extraction solvent enhanced by microwave field, following adsorption by the adsorbent in the micro-solid-phase extraction device. Without any clean-up steps, the extracts were analysed by high performance liquid chromatography coupled with ultra-violet detector. The MAE-μ-SPE approach was developed for the extraction of four tetracycline antibiotics residues in environmental soil, sludge and atmospheric particulate matters. Variables affecting extraction procedures were systematically investigated. Low detection limits of 0.1–6.3 ng/g and low quantification limits of 0.33–20.7 ng/g were achieved under optimised conditions. The recoveries of antibiotics ranged from 70.6% to 110.5% with relative standard deviation of less than 15.1%. The predominance was showed when compared to conventional MAE and μ-SPE method. According to the results, MAE-μ-SPE was proved to be a simple and effective sample preparation method for the analysis of trace organic contaminants in environmental samples.     

加速溶剂萃取-凝胶色谱净化高效液相色谱法测定动物源性食品中的胆固醇

采用加速溶剂萃取-凝胶色谱净化建立了动物源性食品中胆固醇检测的高效液相色谱方法。结果表明,胆固醇浓度在1.0~40.0mg/L范围内线性关系良好,加标回收率为89.1%~99.8%,相对标准偏差为3.1%~7.8%。该方法准确、灵敏度高,适用于富含脂类的动物源性食品中胆固醇的检测。     

基于稀土分离的萃淋树脂制备与应用研究

萃取色层法被称为第二代萃取体系,相对于液-液萃取选择性分离效果更好,萃取剂溶解损失小,被应用于超高纯稀土的制备。萃取色层法的关键是萃淋树脂,决定萃淋树脂性能的关键因素是萃取剂/萃取官能团。按照萃取剂与支撑基底的作用方式不同,萃淋树脂可分为两类:一类是萃取剂通过物理作用负载在支撑物基底上,另一类则是具有萃取作用的官能团通过化学键悬挂在支撑基底上。以萃取剂/萃取官能团为主要切入点,综述了近十年来萃淋树脂的研究进展,阐述了萃淋树脂的制备方法,负载不同萃取剂/悬挂不同萃取官能团的萃淋树脂对RE3+的萃取行为、机制、饱和萃取容量及分离性能等。