Analytical Extraction Methods and Sorbents’ Development for Simultaneous Determination of Organophosphorus Pesticides’ Residues in Food and Water Samples: A Review

Extensive use of organophosphorus pesticides in agriculture leads to adverse effects to the environment and human health. Sample preparation is compulsory to enrich target analytes prior to detection as they often exist at trace levels and this step is critical as it determines the concentration of pollutants present in samples. The selection of a suitable extraction method is of great importance. The analytical performance of the extraction methods is influenced by the selection of sorbents as sorbents play a vital role in the sensitivity and selectivity of an analytical method. To date, numerous sorbent materials have been developed to cater to the needs of selective and sensitive pesticides’ detection. Comprehensive details pertaining to extraction methods, developed sorbents, and analytical performance are provided. This review intended to provide a general overview on different extraction techniques and sorbents that have been developed in the last 10 years for organophosphorus pesticides’ determinations in food and water samples.     

Selective sample treatment using molecularly imprinted polymers

The molecularly imprinted polymers (MIPs) are synthetic polymers possessing specific cavities designed for a target molecule. By a mechanism of molecular recognition, the MIPs are used as selective sorbents for the solid-phase extraction of target analytes from complex matrices. MIPs are often called synthetic antibodies in comparison with immuno-based sorbents; they offer some advantages including easy, cheap and rapid preparation and high thermal and chemical stability. This review describes the use of MIPs in solid-phase extraction with emphasis on their synthesis, the various parameters affecting the selectivity of the extraction, their potential to selectively extract analytes from complex aqueous samples or organic extracts, their on-line coupling with LC and their potential in miniaturized devices.     

Selective extraction of nitroaromatic explosives by using molecularly imprinted silica sorbents

Two molecularly imprinted silicas (MISs) were synthesized and used as selective sorbents for the extraction of nitroaromatic explosives in post-blast samples. The synthesis of the MISs was carried out with phenyltrimethoxysilane as monomer, 2,4-dinitrotoluene (2,4-DNT) as template and triethoxysilane as cross-linker by a sol–gel approach in two molar ratios: 1/4/20 and 1/4/30 (template/monomer/cross-linker). Non-imprinted silica sorbents were also prepared following the same procedures without introducing the template. An optimized procedure dedicated to the selective treatment of aqueous samples was developed for both MISs for the simultaneous extraction of the template and other nitroaromatic compounds commonly used as explosives. The capacity of the MISs was measured by the extraction of increasing amounts of 2,4-DNT in pure water and is higher than 3.2 mg/g of sorbent for each MIS. For the first time, four nitroaromatic compounds were selectively extracted and determined simultaneously with extraction recoveries higher than 79%. The potential of these sorbents was then highlighted by their use for the clean-up of post-blast samples (motor oil, post-mortem blood, calcined fragments, etc.). The results were compared to those obtained using a conventional sorbent, thus demonstrating the interest of the use of these MISs as selective sorbents.     

Recent Progress,Challenges and Prospects in Monitoring Plastic-Derived Xenoestrogens Using Molecularly Imprinted Sorbents

Indoor and outdoor exposure to plastic-derived xenoestrogens, such as phthalates and phenolic compounds, can adversely affect endocrine and reproductive systems in humans and wildlife. To accomplish the extraction of plastic-derived xenoestrogens from environmental samples, molecularly imprinted polymers (MIPs) have been proved to be selective, efficient, and reliable sorbents. Despite some problems associated with the use of MIPs as sorbents, these have been found to be of considerable interest due to their advantages of selectivity, easy synthetic procedures, and better stability over commercially available solid sorbents. Modifications in their synthetic strategies are continuously in progress and new approaches are being made through graphene oxide substrates, nanostructured platforms, nanoferrites, cryogels, and co-electropolymerization to design better sorbents. Apart from this, efforts to create molecularly imprinted solid phase microextraction (SPME) fibers have also been successful in improving the efficiency of the methodology. In future, the use of MIPs developed from advanced synthetic strategies, or as sorbents for more robust techniques like SPME and microextraction on packed sorbents, will add new horizons to explore the potential of MIPs in the field of plastic-derived xenoestrogens. This review presents various challenges, as well as progress and prospects associated with the extraction of plastic-derived phthalates and phenolic compounds using molecularly imprinted sorbents.     

Selective Water Sorbents for Multiple Applications, 10. Energy Storage Ability

The application of new selective water sorbents for storage of low temperature heat is analyzed. Values of energy storage ability E are measured by a DSC technique for more than fifteen samples of selective water sorbents based on silica gels, aluminas, carbon Sibunit and aerogels as host matrices and CaCl₂, LiBr, MgCl₂ as impregnated salts. E-values up to 8.4 kJ/g and 4.0 kJ/g are found for forced and naturally saturated sorbents, which are much higher than for common sorbents, like zeolites and unimpregnated silica gels. The temperature dependence of E gives an estimation of sensible and latent heat contributions as well as the average heat of water desorption and average specific heat of dry sorbents. A comparison between the SWSs and others materials proposed in literature is done.     

Electrospun nanofibers as sorbent material for solid phase extraction

Electrospinning has emerged as the most versatile technique for nanofiber fabrication. Owing to their large surface area to volume ratio, electrospun nanofibers have the potential to serve as a good sorbent material for solid phase extraction (SPE) based techniques. The ability to incorporate a variety of functionalities prior or post-electrospinning presents a platform to tune the sorbents for specific applications. It is the aim of this contribution to highlight some of the recent developments that harness the great potential of electrospun nanofibers as sorbents for SPE. The review discusses the various ways in which the electrospinning technique addresses two important parameters for sorbent material, which are sorptive capacity and selectivity. It concludes by presenting and discussing the potential for development of SPE format technology and configurations based on electrospun nanofibers.     

Extraction of alkyl methylphosphonic acids from aqueous samples using a conventional polymeric solid-phase extraction sorbent and a molecularly imprinted polymer

The analysis of alkyl methylphosphonic acids (AMPAs) constitutes an important subject for verifying the compliance to the Chemical Weapons Convention (CWC). Indeed, alkyl methylphosphonic acids are the degradation products of V and G nerve agents such as VX, sarin or soman. Lowering the limits of detection of analytical methods for complex aqueous matrices implies the introduction of concentration and clean-up steps in the whole analytical process. Therefore a molecular imprinted polymer (MIP) has been previously developed for the selective extraction and the concentration of the alkyl methylphosphonic acids. Unfortunately, the selective retention process on this MIP has involved the development of hydrogen bonds and so does not allow the direct percolation of aqueous samples. A change of solvent is then necessary and can be performed using solid-phase extraction (SPE) with conventional non selective hydrophobic sorbents. Two polymeric sorbents, Oasis HLB and HR-P resins, were selected for their high specific surface area. The extraction recoveries obtained on both sorbents were compared and the Oasis HLB sorbent was further selected and used for the percolation of acidified aqueous samples. An optimised SPE procedure was then applied to concentrate an aqueous soil extract spiked with isobutyl methylphosphonic acid (iBMPA) and cyclopentyl methylphosphonic acid (cPMPA) that was further cleaned-up by passing through the MIP. The resulting LC-MS full scan chromatograms highlight the clean-up effect of the SPE-MIP association by the removal of the matrix substances and the preservation of 95% of the compounds of interest.     

Chemically modified polymeric sorbents for sample preconcentration

Solid-phase extraction is an attractive alternative in sample preparation because it overcomes many drawbacks of liquid-liquid extraction and makes on-line determination possible by hyphenation with chromatographic techniques. Driven by the need for more effective and more selective sorbents, advances in solid-phase extraction include the development of new materials. This paper describes different types of chemically modified sorbents for the solid-phase extraction of compounds from aqueous samples. Chemical introduction of different functional groups into a polymeric resin improves the efficiency of solid-phase extraction by providing better surface contact with the aqueous samples; also, these sorbents have a greater capacity than the typical solid-phase materials for polar compounds have. The most important new sorbents are the chemically modified resins based on styrene-divinylbenzene copolymers. Preparation of these new sorbents is described, and advantages and drawbacks of off-line procedures and on-line procedures are also discussed. Applications for off-line and on-line chromatographic determinations of polar compounds are presented.     

双模板铅离子印迹吸附剂的制备及其应用于环境水及沉积物样品中铅的选择性吸附

利用溶胶-凝胶法制备了一种双模板介孔Pb2+印迹吸附剂(Pb-CTMAB-imp).通过平衡吸附实验,研究了Pb-CTMAB-imp的吸附性能和对Pb2+的选择识别性能.结果表明,Cd2+存在时,Pb-CTMAB-imp对Pb2+的选择系数可以达到91,远高于只用十六烷基三甲基溴化铵(CTMAB)作为模板的印迹吸附剂(...     

Development of imprinted materials for the selective extraction of nitroaromatic explosives

Molecularly imprinted sorbents were synthesized and used as selective extraction sorbents for the analysis of nitroaromatic explosives. Their synthesis by radical polymerization using organic monomers and by sol–gel approach using organosilanes was considered to develop a selective sorbent. The sol–gel approach with phenyltrimethoxysilane (PTMS) as monomer and 2,4-dinitrotoluene (2,4-DNT) as template gave the most promising results. An optimized procedure adapted to the selective treatment of aqueous samples was then developed and applied to various target explosives. For the first time four nitroaromatic compounds were retained on the molecularly imprinted silica (MIS) with extraction recoveries between 29% and 81%, while only low recoveries were obtained on the non-imprinted sorbent, thus highlighting the high degree of selectivity. The MIS was then used for the clean-up of a sample containing motor oil spiked with 2,4-DNT and 2,4,6-trinitrotoluene (2,4,6-TNT). The results were compared with those obtained using a conventional sorbent (Oasis HLB). The cleanest chromatogram obtained using the MIS emphasized the high potential of the MIS as selective sorbent.     

Hypercrosslinked strong anion‐exchange resin for extraction of acidic pharmaceuticals from environmental water

Two novel high‐specific surface area polymeric sorbents (HXLPP‐SAXa and HXLPP‐SAXb) were synthesised and evaluated as solid‐phase extraction sorbents. The novel sorbents under study are based on hypercrosslinked polymer microspheres and designed specifically to offer ion‐exchange properties; the specific polymers of interest in the current work have been chemically modified in such a way as to impart a tuneable level of strong anion‐exchange character onto the sorbents. The novel sorbents were applied as strong anion‐exchange sorbents in solid‐phase extraction studies, with the goal being to selectively extract a group of acidic compounds from complex environmental samples in an efficient manner. Out of two HXLPP‐SAX resins evaluated in this study, it was found that the sorbent with the lower ion‐exchange capacity (HXLPP‐SAXa) gave rise to the best overall performance characteristics and, indeed, was found to compare favourably to the solid‐phase extraction performance of commercial strong anion‐exchange sorbents. When the HXLPP‐SAXa sorbent was applied to the solid‐phase extraction of environmental water samples, the result showed quantitative and selective extraction of low levels of acidic pharmaceuticals from 500 mL of river water and 100 mL of effluent wastewater.     

Determination of bisphenols in sewage based on supramolecular solid-phase extraction/liquid chromatography/fluorimetry

Supramolecular sorbents (hemimicelles/admicelles) are proposed for the extraction/preconcentration of bisphenols from aqueous environmental samples prior to their liquid chromatography/fluorimetric determination. A comparative study on the use of cetyltrimethylammonium bromide (CTABr)-coated silica and sodium dodecyl sulphate (SDS)-coated gamma-alumina as sorbent materials, is presented. Bisphenol A (BPA) and bisphenol F (BPF) were quantitatively retained on CTABr admicelles. Addition of tetrabutylammonium chloride (TBAC) to water samples was required to completely retain bisphenols on SDS-gamma-alumina. Retention on both sorbents occurred through hydrophobic and pi-cation interactions between the quaternary ammonium head group of the cationic amphiphile (CTABr or TBAC) and the aromatic rings of the target analytes. TBAC-SDS-gamma-alumina was the sorbent selected for the SPE of bisphenols on the basis of the lower elution volume required (1 ml of methanol) and the greater breakthrough volume allowed (400 ml), which permitted to reach practical detection limits of 10 and 15 ng/l for BPF and BPA, respectively. The proposed method was used to quantify bisphenol A and bisphenol B in wastewater samples from four sewage treatment plants. Recoveries obtained ranged between about 99 and 105% for raw wastewater and between 96 and 106% for treated wastewater.     

Determination of ofloxacin and lomefloxacin in chicken muscle using molecularly imprinted solid-phase extraction coupled with liquid chromatography

A new molecularly imprinted solid-phase extraction (MISPE) procedure combined with liquid chromatography was developed for the simultaneous selective extraction and determination of ofloxacin (OFL) and lomefloxacin (LOM) in chicken muscle samples. The water-compatible molecularly imprinted microspheres (MIMs) were synthesized by aqueous suspension polymerization using 2-hydroxy-3-naphthoic acid and 1-methylpiperazine as mimic templates. The MIMs applied as selective sorbents in SPE method showed high selectivity and affinity to OFL and LOM in complex biological matrices. Good linearity was obtained in a range of 0.025-2.0 μg/g, and the average recoveries of OFL and LOM at three spiked levels ranged from 94.4 to 96.9%, respectively, with the relative standard deviation ≤4.7%. The developed MISPE-HPLC method was successfully applied to the isolation of OFL and LOM in chicken muscles, which demonstrated the potential ability of the novel MIMs for selective extraction of fluoroquinolones in biological samples.     

汞离子天然吸附剂

汞离子是现代工业中剧毒的污染物之一,研究者致力于汞离子高效吸附剂的研制已有多年.本文基于国内外最新研究文献,系统论述了汞离子天然吸附剂如壳聚糖、矿物、微生物及其改性材料等的吸附性能,并详细比较了各种吸附剂的优缺点,指出天然吸附剂来源广泛、价格便宜,尤其是修饰后的壳聚糖吸附性能甚至可以和一些合成吸附剂相媲美.在所报道的天然吸附剂中,引入巯基后的戊二醛交联壳聚糖,对初始浓度为500 mg/L的汞离子的吸附容量可达1 604.7mg/g,属已知的汞离子天然吸附剂中之最.天然汞离子吸附剂在工业废水处理中显示出了广阔的应用前景.     

Evaluation of metal fractions in river sediments and waters: application of chelation chromatography-differential pulse anodic stripping voltammetry

The ability of chelation chromatography in combination with differential pulse anodic stripping voltammetry (DPASV) to provide a simple, fast and reliable way of dealing with interionic interferences, competitive complexations, re-adsorption of released metal ions and sorption of spiking metal ions by organic/inorganic materials in the complex matrixes of real natural samples has been critically examined. The technique is based on the selective complexation of target metal fractions on some novel sorbents which are polymeric chelating resins doped on stationary supports (Whatman No. 1 paper and silica gel). The usual complications of leaching of the resin and/or the chelating ligand and colloid retention on the sorption bed at any stage of separation were largely obviated with these sorbents under the operational conditions of metal sorption. A detailed study on the application of such sorbents to the differentiation of ionic (free), labile (ionic plus weakly complexed) and bound (strongly complexed) metal fractions present in local river-sediment and water samples was carried out. Chelating resin-impregnated paper (CRIP) and chelating resin-immobilized silica gel column (CRISC) methods of chromatographic separation of analyte trace metals in combination with the follow-up 'standard addition' procedure of the DPASV technique were employed. A modest attempt has been made to formulate a speciation (fractionation) scheme for metal contents present in river-sediments and waters on the basis of selective retention of ionic and labile fractions on complexing resins.     

Poly(styrene‐co‐N‐methacryloyl‐l‐phenylalanine methyl ester)‐functionalized magnetic nanoparticles as sorbents for the analysis of sodium benzoate in beverages

In this study, poly(styrene‐co‐N‐methacryloyl‐l ‐phenylalanine methyl ester)‐functionalized magnetic nanoparticles were constructed and used as magnetic solid‐phase extraction sorbents for analysis of food preservatives in beverages. To prepare the poly(amino acid)‐based sorbents, N‐methacryloyl‐l ‐phenylalanine methyl ester, and styrene served as the functional monomers and modified onto the magnetic nanoparticles via free radical polymerization. Interestingly, compared with propylparaben and potassium sorbate, the proposed poly(amino acid)‐based sorbents showed a good selectivity to sodium benzoate. The adsorption capacity of the sorbents to sodium benzoate was 6.08 ± 0.31 mg/g. Moreover, the fast adsorption equilibrium could be reached within 5 min. Further, the resultant poly(amino acid)‐based sorbents were applied in the analysis of sodium benzoate in real beverage samples. The results proved that the proposed magnetic solid‐phase extraction sorbents have a great potential for the analysis of preservatives in food samples.     

Sorption of radionuclides on inorganic sorbents

Inorganic sorbents are often used in separation of metals and radionuclides in radioanalytical application and they were also used in technological scale for separation of radionuclides in cleanup of Three Mile Island NPP. Inorganic sorbents become popular in the last years because no problem with organic contamination, there are stable against radiation, sorption efficiency can be tailor made for selective separation of chosen metal. Contrary to the organic sorbents they have usually lower capacity and chemical stability is limited to narrower pH. Nevertheless of some problems, many good properties of inorganic sorbents make them very attractive for sorption study.     

Surface modified‐magnetic nanoparticles by molecular imprinting for the dispersive solid‐phase extraction of triazines from environmental waters

Magnetic nanoparticles have been surface modified by molecular imprinting and evaluated as selective sorbents for the extraction of triazines from environmental waters. The use of propazine as template allowed us to synthesize a selective material able to simultaneously recognize and selective extract not only the template but also several other herbicides of the same family. A magnetic molecularly imprinted‐based dispersive solid‐phase extraction procedure was developed and fully optimized. Magnetic molecularly imprinted polymer particles can be easily collected and separated from liquid solvents and samples with the help of an external magnetic field, avoiding in that way any centrifugation or filtration steps, which represents a remarkable advantage over traditional procedures. Under optimum conditions, selective extraction of several triazines (cyanazine, simazine, atrazine, propazine, and terbutylazine) from environmental water samples was performed prior to final determination by high‐performance liquid chromatography with diode‐array detection. Recoveries for the studied triazines were within the range of 75.2–94.1%, with relative standard deviations lower than 11.3% (n = 3). The limits of detection were within 0.16–0.51 µg/L, depending upon the triazine and the type of sample analyzed.     

Specific mercury(II) adsorption by thymine-based sorbent

A new kind of polymer sorbent based on the specific interaction of Hg(II) with nucleic acid base, thymine, is described for the selective adsorption of Hg(II) from aqueous solution. Two types of sorbents immobilized with thymine were prepared by one-step swelling and polymerization and graft polymerization, respectively. The maximum static adsorption capacity of the new polymer sorbents for Hg(II) is proportional to the density of thymine on their surface, up to 200 mg/g. Moreover, the new kind polymer sorbent shows excellent selectivity for Hg(II) over other interfering ions, such as Cu(II), Cd(II), Zn(II), Co(II), Ca(II) and Mg(II), exhibits very fast kinetics for Hg(II) adsorption from aqueous solution, and can be easily regenerated by 1.0 M HCl. It also has been successfully used for the selective adsorption of spiked Hg(II) from real tap water samples. This new thymine polymer sorbent holds a great promise in laboratory and industrial applications such as separation, on-line enrichment, solid-phase extraction, and removal of Hg(II) from pharmaceutical, food and environmental samples.     

Molecularly Imprinted Polymers for Stir Bar Sorptive Extraction: Synthesis,Characterization, and Application

Stir bar sorptive extraction is widely used for the preconcentration of organic and inorganic compounds due to its simplicity and versatility. However, commercially available devices are based on nonselective sorbents. Molecularly imprinted polymers provide selective recognition abilities from the template employed during their preparation. In this review, strategies employed for recent for molecularly imprinted polymers employed in stir bar sorptive extraction are described. The advantages and disadvantages are described, as well as future trends involving this preconcentration methodology.