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1.
Analytical potentiality of a modified version of the QuEChERS (Quick, Easy, Cheap, Effective, Rugged and Safe) method has been studied and validated for the extraction of a group of 11 pesticides (ethoprophos, cadusafos, dimethoate, terbufos, disulfoton, chlorpyrifos‐methyl, fenitrothion, pirimiphos‐methyl, malathion, chlorpyrifos and fensulfothion) and some of their metabolites (malaoxon, disulfoton sulfoxide, terbufos sulfone and disulfoton sulfone) in toasted barley and chickpea flours. The method involves separation and quantification by gas chromatography (GC) with nitrogen phosphorus detection (NPD) using triphenylphosphate as the internal standard. Matrix‐matched calibration was carried out for both flours due to the existence of a matrix effect. Linearity, recovery, precision and accuracy studies of the proposed QuEChERS‐GC‐NPD method were evaluated in each sample matrix. Mean recovery values were in the range of 73–118% with relative standard deviation values below 10%. Limits of detection of the whole method were between 0.07 and 57.39 μg/kg. The method was finally applied for the analysis of 14 samples collected in different zones of the Tenerife island. The residues of pirimiphos‐methyl were found in 13 of them, confirming its unequivocal presence by mass spectrometry.  相似文献   

2.
In this work, the simultaneous separation of a group of 12 pesticides (carbaryl, fensulfothion, mecoprop, fenamiphos, haloxyfop, diclofop, fipronil, profenofos, fonofos, disulfoton, nitrofen, and terbufos) by nano-liquid chromatography with UV detection is described. For the analyses, a 100 μm internal diameter capillary column packed with silica modified with phenyl groups was used. Experimental parameters, including the use of a trapping column for increasing the sensitivity, were optimized and validated. A preliminary study of the applicability of a rapid and practical dispersive solid-phase extraction (DSPE) procedure was developed for the extraction of some of these pesticides (carbaryl, fensulfothion, fenamiphos, fipronil, profenofos, fonofos, disulfoton, nitrofen, and terbufos) from Milli-Q water samples using multi-walled carbon nanotubes (MWCNTs). The method was validated through a recovery study at three different levels of concentration, obtaining limits of detection in the range 0.016–0.067 μg/L (below European Union maximum residue limits) for the majority of the pesticides. In this work, MWCNTs were reused up to five times, representing an important reduction of the waste of stationary phase. Furthermore, DSPE permitted a clear diminution of the total sample treatment time with respect to conventional SPE.  相似文献   

3.
Multiwalled carbon nanotubes with exceptional merits as SPE adsorbents for enrichment of environmental pollutants have absorbed much attention. The goal of this paper was to make a comparison with it and regular adsorbents such as C18 silica and activated carbon in the extraction capacity of atrazine and simazine. The results indicated that multiwalled carbon nanotubes were very suitable for determination of atrazine and simazine because of an enrichment performance similar to that of C18 silica. In contrast, the spiked recovery of simazine was higher than that of atrazine using multiwalled carbon nanotubes as packing material for SPE. However, reverse results were obtained when the extraction was performed with packing of C18 silica. Moreover, as the extraction of simazine was concerned, multiwalled carbon nanotubes were much better than C18 silica. As for the enrichment of atrazine, C18 silica achieved greater extraction factor than multiwalled carbon nanotubes. Activated carbon did not give the expected extraction efficiency because of its large size and blank volume and less active sites for adsorption. All these experimental results indicated that multiwalled carbon nanotubes could be used as a valuable alternative adsorbent for SPE of atrazine and simazine in many real water samples.  相似文献   

4.
基于超高效液相色谱-串联质谱(UHPLC-MS/MS)建立定量分析乙拌磷及其5个代谢物(乙拌磷砜、乙拌磷亚砜、内吸磷-S、内吸磷-S-砜、内吸磷-S-亚砜)的方法,应用该方法分析其在农产品(豌豆、芦笋、小麦、咖啡豆和花生)中的残留量。对样品前处理及色谱条件进行优化,样品经过乙腈涡旋提取(小麦、咖啡豆和花生先加水润湿),经盐析分层,取上清液经50 mg C18、50 mg PSA和50 mg NH2混合分散固相萃取净化后,经Thermo Syncronis C18色谱柱(150 mm×2.1 mm, 5 μm)分离,柱温40 ℃,进样量2 μL,以水和乙腈为流动相梯度洗脱后,采用ESI源,在正离子扫描和多反应监测(MRM)模式下检测,外标法定量。结果表明,乙拌磷及其代谢物在2.0~200.0 μg/L范围内线性关系良好,相关系数(R2)≥0.9981。方法的检出限(LOD)为0.02~2.0 μg/kg,并以最小添加水平5 μg/kg为定量限(LOQ)。乙拌磷及其代谢物在豌豆、芦笋、小麦、咖啡豆和花生中5、100、1000 μg/kg 3个添加水平下的平均回收率为75.0%~110.0%,相对标准偏差(RSD)为0.7%~14.9%,方法的准确度和精密度符合农药残留测定。应用建立的方法对市售的40份小麦样品和40份花生样品进行检测,均低于方法的检出限。该方法具有操作简单、快速、灵敏、准确的特点,适用于谷物、油料、蔬菜等多种农产品中乙拌磷及其代谢物的残留检测。  相似文献   

5.
A microdispersive solid‐phase extraction method has been developed using multiwalled carbon nanotubes of 110–170 nm diameter and 5–9 μm length for the extraction of a group of nine phthalic acid esters (i.e., bis(2‐methoxyethyl) phthalate, bis‐2‐ethoxyethyl phthalate, dipropyl phthalate, butylbenzyl phthalate, bis‐2‐n‐butoxyethyl phthalate, bis‐isopentyl phthalate, bis‐n‐pentyl phthalate, dicyclohexyl phthalate, and di‐n‐octyl phthalate) from tap water as well as from different beverages commercialized in plastic bottles (mineral water, lemon‐ and apple‐flavored mineral water, and an isotonic drink). Determination was carried out by high‐performance liquid chromatography coupled to mass spectrometry. The extraction procedure was optimized following a step‐by‐step approach, being the optimum extraction conditions: 50 mL of each sample at pH 6.0, 80 mg of sorbent, and 25 mL of acetonitrile as elution solvent. To validate the methodology, matrix‐matched calibration and a recovery study were developed, obtaining determination coefficients >0.9906 and absolute recovery values between 70 and 117% (with relative standard deviations < 17%) in all cases. The limits of quantification of the method were between 0.173 and 1.45 μg/L. After the evaluation of the matrix effects, real samples were also analyzed, finding butylbenzyl phthalate in all samples (except in apple‐flavored mineral water), though at concentrations below its limit of quantification of the method.  相似文献   

6.
Zhou Q  Xiao J  Wang W  Liu G  Shi Q  Wang J 《Talanta》2006,68(4):1309-1315
Multiwalled carbon nanotubes, a new nanoscale material, has been gained many interests for use in various fields, and has exhibited exceptional merit as SPE absorbents for enrichment of environmental pollutants. This paper focused on the enriching power of atrazine and simazine, two important widely used triazine herbicides and described a novel and sensitive method for determination of these two herbicides based on SPE using multiwalled carbon nanotubes as solid phase absorbents followed by high performance liquid chromatography with diode array detector. Factors that maybe affect the enrichment efficiency of multiwalled carbon nanotubes such as the volume of eluent, sample flow rate, sample pH, and volume of the water samples were optimized. Under the optimal procedures, multiwalled carbon nanotubes as the absorbents have obtained excellent enrichment efficiency for atrazine and simazine. The detection limits of the atrazine and simazine were 33 and 9 ng l−1, respectively. The spiked recoveries of the two analytes were over the range of 82.6-103.7% in most cases. Good analytical performance was achieved from real-world water samples such as river water, reservoir water, tap water and wastewater after primary pretreatment with proposed method. All these experimental results indicated that the developed method could be used as an alternative for the routine analysis of atrazine and simazine in many real water samples.  相似文献   

7.
In the present study, a new analytical method has been developed for the simultaneous quantification of 15 organophosphorus pesticides, including some of their metabolites, (disulfoton-sulfoxide, ethoprophos, cadusafos, dimethoate, terbufos, disulfoton, chlorpyrifos-methyl, malaoxon, fenitrothion, pirimiphos-methyl, malathion, chlorpyrifos, terbufos-sulfone, disulfoton-sulfone and fensulfothion) in three different types of commercial cereal-based baby foods. Dispersive solid-phase extraction (dSPE) with multi-walled carbon nanotubes (MWCNTs) was used together with gas chromatography with nitrogen phosphorus detection. Most favorable conditions involved a previous ultrasound-assisted extraction of the sample with acetonitrile containing formic acid. After evaporation of the extract and redissolution in water, a dSPE procedure was carried out with MWCNTs. The whole method was validated in terms of repeatability, linearity, precision and accuracy and matrix effect was also evaluated. Absolute recoveries were in the range 64-105 % with relative standard deviation values below 7.6 %. Limits of quantification achieved ranged from 0.31 to 5.50 μg/kg, which were lower than the European Union maximum residue limits for pesticide residues in cereal-based baby foods.  相似文献   

8.
An analytical method based on dispersive solid‐phase extraction with a multiwalled carbon nanotubes sorbent coupled with positive pulse glow discharge ion mobility spectrometry was developed for analysis of 30 pesticide residues in drinking water samples. Reduced ion mobilities and the mass–mobility correlation of 30 pesticides were measured. The pesticides were divided into five groups to verify the separation capability of pulse glow discharge in mobility spectrometry. The extraction conditions such as desorption solvent, ionic strength, conditions of adsorption and desorption, the amounts of multiwalled carbon nanotubes, and solution pH were optimized. The enrichment factors of pesticides were 5.4‐ to 48.7‐fold (theoretical enrichment factor was 50‐fold). The detection limits of pesticides were 0.01~0.77 μg/kg. The linear range was 0.005–0.2 mg/L for pesticide standard solutions, with determination coefficients from 0.9616 to 0.9999. The method was applied for the analysis of practical and spiked drinking water samples. All results were confirmed by high‐performance liquid chromatography with tandem mass spectrometry. The proposed method was proven to be a commendably rapid screening qualitative and semiquantitative technique for the analysis of pesticide residues in drinking water samples on site.  相似文献   

9.
Multiwalled carbon nanotubes functionalized by oxidation of original multiwalled carbon nanotubes with NaClO were prepared and their application as solid phase extraction sorbent for 2,4-dichlorophenoxyacetic acid (2,4-D) was investigated systemically, and a new method was developed for the determination of trace 2,4-D in water samples based on extraction and preconcentration of 2,4-D with solid phase extraction columns packed with NaClO-treated multiwalled carbon nanotubes prior to its determination by HPLC. The optimum experimental parameters for preconcentration of 2,4-D, including the column activating conditions, the amount of the sorbent, pH of the sample, elution composition, and elution volume, were investigated. The results indicated 2,4-D could be quantitatively retained by 100 mg NaClO-treated multiwalled carbon nanotubes at pH 5, and then eluted completely with 10 mL 3:1 (v/v) methanol-ammonium acetate solution (0.3 mol/L). The detection limit of this method for 2,4-D was 0.15 μg/L, and the relative standard deviation was 2.3% for fortified tap water samples and 2.5% for fortified riverine water sample at the 10 μg/L level. The method was validated using fortified tap water and riverine water samples with known amount of 2,4-D at the 0.4, 10, and 30 μg/L levels, respectively.  相似文献   

10.
A headspace solid‐phase microextraction method was developed for the preconcentration and extraction of methyl tert‐butyl ether. An ionic‐liquid‐mediated multiwalled carbon nanotube–poly(dimethylsiloxane) hybrid coating, which was prepared by covalent functionalization of multiwalled carbon nanotubes with hydroxyl‐terminated poly(dimethylsiloxane) using the sol–gel technique, was used as solid‐phase microextraction adsorbent. This innovative fiber exhibited a highly porous surface structure, high thermal stability (at least 320°C) and long lifespan (over 210 uses). Potential factors affecting the extraction efficiency were optimized. Under the optimum conditions, the method LOD (S/N = 3) was 0.007 ng/mL and the LOQ (S/N = 10) was 0.03 ng/mL. The calibration curve was linear in the range of 0.03–200 ng/mL. The RSDs for one fiber (repeatability, n = 5) at three different concentrations (0.05, 1, and 150 ng/mL) were 5.1, 4.2, and 4.6% and for the fibers obtained from different batches (reproducibility, n = 3) were 6.5, 5.9, and 6.3%, respectively. The developed method was successfully applied to the determination of methyl tert‐butyl ether in different real water samples on three consecutive days. The relative recoveries for the spiked samples with 0.05, 1, and 150 ng/mL were between 94–104%.  相似文献   

11.
In the present work, a GC method with nitrogen-phosphorus detection (NPD) was developed for the simultaneous determination of eight organophosphorus pesticide (OPP) residues (i.e., ethoprofos, diazinon, chlorpyrifos-methyl, fenitrothion, malathion, chlorpyrifos, fenamiphos, and buprofezin) in water samples. Preconcentration of the water samples was carried out using an SPE procedure with multiwalled carbon nanotubes (MWCNTs) of 10-15 nm od, 2-6 nm id, and 0.1-10 microm length as stationary phase. Extraction parameters, such as the amount of MWCNTs, sample volume, pH, and type and amount of the eluent were optimized. The most favorable conditions were as follows: 40 mg MWCNTs, 800 mL water, pH 6.0, and 20 mL dichloromethane, respectively. The MWCNTs-SPE-GC-NPD method was applied to the determination of these pesticides in real water samples: mineral and ground water as well as run-off water from an agricultural area collected shortly before opening out onto the sea. A recovery study was developed with five consecutive extractions of the three types of water spiked at three concentration levels (n = 15). Mean recovery values were in the range of 75-116% for mineral water (RSD < 6.3%), 67-119% for ground water (RSD < 5.8%), and 57-81% for run-off waters (RSDs < 6.9%), except for fenamiphos (mean recovery values between 40 and 84% for the three types of waters, RSDs < 8.9%). LODs were in the low ng/L level (i.e., levels below the maximum residue limits (MRLs) established by the European Union (EU) legislation for these compounds in waters). The proposed method was also applied to the analysis of six water samples (two of each type: mineral, ground, and run-off waters) in which no residues of the selected pesticides were found. Results show that the MWCNTs used in this work have a high adsorbability of the pesticides under study. The main advantage of the use of these MWCNTs is their low cost when compared with those MWCNTs previously used in the literature and with conventional SPE cartridges.  相似文献   

12.
Recently, multiwalled carbon nanotubes (MWCNTs) have been at the center of attention because of their applications in many fields. Efforts to investigate the possibility of MWCNTs as SPE absorbents for the enrichment of environmental pollutants yielded positive results. The goal of the present work was to compare the enrichment power of MWCNTs with that of regular adsorbents, such as C18 silica for SPE of five sulfonylurea herbicides. The results indicated that multiwalled carbon nanotubes were very suitable for the preconcentration of sulfonylurea herbicides in complex water samples, yielding better recoveries. C18 gave a lightly lower enrichment performance, and could not enrich nicosulfuron in complex samples. All of these experimental results indicated that multiwalled carbon nanotubes could be used as a valuable alternative adsorbent for the SPE of sulfonylurea herbicides in many real water samples.  相似文献   

13.
Solid-phase extraction and gas chromatography with electron-capture detection has been used for sensitive, simple, and reliable analysis of carfentrazone-ethyl residues in water. Carfentrazone-ethyl was enriched by use of multiwalled carbon nanotubes (MWCNT), a new adsorptive material. Several conditions affecting recovery of the analyte, for example polarity and volume of eluents, pH of water samples, and sample volume, were studied. Recovery from fortified samples, linear range, and limit of detection were evaluated. The results showed that MWCNT are an efficient SPE adsorbent for preconcentration of carfentrazone-ethyl in water. Under the optimized SPE conditions, recovery of carfentrazone-ethyl from fortified water was 81.49–91.08%, with RSD from 1.66 to 8.21%. The limits of detection and quantification were 0.01 and 0.03 µg L?1, which were lower than the MRL stipulated by the EU for individual pesticides in water (0.1 µg L?1). Finally, the method was applied to tap water and river water; the results showed that the method was suitable for detection of carfentrazone-ethyl in environmental water samples.  相似文献   

14.
In this work, a simple and environmental friendly methodology has been developed for the analysis of a group of six mycotoxins with estrogenic activity produced by Fusarium species (i.e. zearalanone, zearalenone, α‐zearalanol, β‐zearalanol, α‐zearalenol, and β‐zearalenol), using microdispersive SPE (μ‐dSPE) with multiwalled carbon nanotubes as sorbent. Separation, determination, and quantification were achieved by HPLC coupled to ion trap MS with an ESI interface. Parameters affecting the extraction efficiency of µ‐dSPE such as pH of the sample, amount of multiwalled carbon nanotubes, and type and volume of elution solvent, were studied and optimized. The methodology was validated for mineral, pond, and wastewater as well as for powdered infant milk using 17β‐estradiol‐2,4,16,16,17‐d5 (17β‐E2‐D5) as internal standard, obtaining recoveries ranging from 85 to 120% for the three types of water samples and from 77 to 115% for powdered infant milk. RSD values were lower than 10%. The LOQs achieved were in the range 0.05–2.90 μg/L for water samples and 2.02–31.9 μg/L for powdered infant milk samples.  相似文献   

15.
A new method using multiwalled carbon nanotubes as an SPE adsorbent was developed for the sensitive determination of trace iron and lead prior to flame atomic absorption spectrometry analysis. Iron and lead as 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline chelates were adsorbed quantitatively on multiwalled carbon nanotubes at a pH of 6.0 and easily eluted with 10 mL 1 M HNO3. The influences of matrix ions were also examined. The LOD values for iron and lead were calculated as 1.3 and 2.9 microg/L, respectively. Validation of the presented procedure was performed by the analysis of TMDA 54.4 fortified lake water and HR-1 Humber River sediment certified reference materials. The method was successfully applied to the determination of trace iron and lead in real environmental samples, and excellent results were achieved.  相似文献   

16.
Although jujube is a minor crop and very few pesticides are registered on it, the application of pesticides during the growth stage of jujube is inevitable to control the pests or diseases. This situation has led to pesticide misuse. A modified quick, easy, cheap, effective, rugged, and safe method using a novel sorbent, multiwalled carbon nanotubes, as a dispersive solid‐phase extraction sorbent combined with gas chromatography with mass spectrometry, was developed for the determination of 16 pesticides in jujube. Under the optimized conditions, recoveries of 76.7–112.4% were obtained for the target analytes at three spiked concentration levels. The relative standard deviations ranged from 1.2 to 12.3%. Limits of detection and limits of quantification for 16 pesticides ranged from 1 to 10 and 3 to 30 μg/kg, respectively. The residues of chlorpyrifos, hexaconazole, tebuconazole, and cyhalothrin were detected from samples obtained from the market.  相似文献   

17.
Multi-walled carbon nanotubes (MWCNs) are used as adsorbent for solid-phase extraction (SPE) of several chlorophenols (CPs). CPs were adsorbed on MWCNs cartridge, then desorbed with pH 10.0 methanol, finally determined by HPLC. Under the optimized conditions, detection limits of 0.08-0.8 ng mL(-1) were obtained. The method had been applied to analyze the five CPs in tap water and river water.  相似文献   

18.
In this paper, multiwalled‐carbon‐nanotube‐based matrix solid‐phase dispersion coupled to HPLC with diode array detection was used to extract and determine honokiol and magnolol from Magnoliae Cortex. The extraction efficiency of the multiwalled‐carbon‐nanotube‐based matrix solid‐phase dispersion was studied and optimized as a function of the amount of dispersing sorbent, volume of elution solvent, and flow rate of elution solvent, with the aid of response surface methodology. An amount of 0.06 g of carboxyl‐modified multiwalled carbon nanotubes and 1.5 mL of methanol at a flow rate of 1.1 mL/min were selected. The method obtained good linearity (r2 > 0.9992) and precision (RSD < 4.7%) for honokiol and magnolol, with limits of detection of 0.045 and 0.087 μg/mL, respectively. The recoveries obtained from analyzing in triplicate spiked samples were determined to be from 90.23 to 101.10% and the RSDs from 3.5 to 4.8%. The proposed method that required less samples and reagents was simpler and faster than Soxhlet and maceration extraction methods. The optimized method was applied for analyzing five real samples collected from different cultivated areas.  相似文献   

19.
A fast, sensitive, and convenient technique consisting of a miniaturized solid‐phase extraction method named microextraction in packed syringe coupled with gas chromatography and mass spectrometry was developed for the preconcentration and determination of some pesticides, including hexachlorobenzene, heptachlor, alachlor, aldrine, and metolachlore, in natural water samples. Carboxyl‐purified multiwalled carbon nanotubes were used as a sorbent in microextraction in packed syringe. Based on this technique, 6.0 mg of multiwalled carbon nanotubes was inserted in the syringe between two polypropylene frits. The analytes would be adsorbed on the solid phase, and would subsequently be eluted using organic solvents. The influence of some important parameters involved including the solution pH, type, and volume of the organic desorption solvent, and amount of the multiwalled carbon nanotubes sorbent on the extraction efficiency of the selected pesticides were investigated. The proposed method showed a good linearity in the range of 0.1–25.0 ng/mL and low limits of detection in the range of 0.02–0.19 ng/mL using the selected ion‐monitoring mode. Reproducibility of the method was in the range of 3.3–8.5% for the studied pesticides. Also to evaluate the matrix effect, the developed method was applied to the preconcentration and determination of the selected pesticides in different water samples.  相似文献   

20.
SPE combined with dispersive liquid–liquid microextration was used for the extraction of ultra‐trace amounts of benzodiazepines (BZPs) including, diazepam, midazolam, and alprazolam, from ultra‐pure water, tap water, fruit juices, and urine samples. The analytes were adsorbed from large volume samples (60 mL) onto octadecyl silica SPE columns. After the elution of the desired compounds from sorbents with 2.0 mL acetone, 0.5 mL of eluent containing 40.0 μL chloroform was injected rapidly into 4.5 mL pure water. After extraction and centrifugation, 2 μL of the sedimented phase was injected into a GC equipped with a flame ionization detector. Several parameters affecting this process were investigated and optimized. Under the optimal conditions, LODs ranged from 0.02 to 0.05 μg/L, a linear dynamic range of 0.1–100 μg/L and relative SDs in the range of 4.4–10.7% were attained. Very high preconcentration factors ranging from 3895–7222 were achieved. The applicability of the method for the extraction of BZPs from different types of complicated matrices, such as tap water, fruit juices, and urine samples, was studied. The obtained results reveal that the proposed method is a good technique for the extraction and determination of BZPs in complex matrices.  相似文献   

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