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1.
Extraction, enrichment and gas chromatography mass spectrometric analysis of degradation products of nerve agents from water is of significant importance for verification of Chemical Weapons Convention (CWC) and gathering forensic evidence of use of nerve agents. Multi-walled carbon nanotubes (MWCNTs) were non-covalently functionalized with poly(diallyldimethylammonium chloride) (PDDA) to afford the cationic functionalized nano-tubes, which were used as solid-phase anionic-exchanger sorbents to extract the acidic degradation products of nerve agents from water. Extraction efficiencies of MWCNTs-PDDA were compared with those of mixed mode anion-exchange (HLB) and silica based strong anion-exchange (Si-SAX) cartridges. Optimized extraction parameters included MWCNTs-PDDA 12 mg, washing solvent 5 mL water and eluting solvent 3 mL of 0.1M aqueous HCl followed by 3 mL methanol. At 1 ng mL(-1) spiking concentration of mono- and di-basic phosphonic acids, MWCNTs-PDDA exhibited higher extraction efficiencies in comparison to Si-SAX and HLB. The limits of detection were achieved down to 0.05 and 0.11 ng mL(-1) in selected ion and full scan monitoring mode respectively; and limits of quantification in selected ion monitoring mode were achieved down to 0.21 ng mL(-1).  相似文献   

2.
Su R  Wang X  Xu X  Wang Z  Li D  Zhao X  Li X  Zhang H  Yu A 《Journal of chromatography. A》2011,1218(31):5047-5054
The multiwall carbon nanotubes (MWCNTs)-based matrix solid phase dispersion (MSPD) was applied for the extraction of hormones, including 17-α-ethinylestradiol, 17-α-estradiol, estriol, 17-β-estradiol, estrone, medroxyprogesterone, progesterone and norethisterone acetate in butter samples. The method includes MSPD extraction of the target analytes from butter samples, derivatization of hormones with heptafluorobutyric acid anhydride-acetonitrile mixture, and determination by gas chromatography-mass spectrometry. The mixture containing 0.30 g graphitized MWCNTs and 0.10 g MWCNTs was selected as absorbent. Ethyl acetate was used as elution solvent. The elution solvent volume and flow rate were 12 mL and 0.9 mL min(-1), respectively. The recoveries of hormones obtained by analyzing the five spiked butter samples were from 84.5 to 111.2% and relative standard deviations from 1.9 to 8.9%. Limits of detection and quantification for determining the analytes were in the range of 0.2-1.3 and 0.8-4.5 μg kg(-1), respectively. Compared with other traditional methods, the proposed method is simpler in the operation and shorter in the sample pretreatment time.  相似文献   

3.
The analysis of nitrogen containing amino alcohols, which are the precursors and degradation products of nitrogen mustards and nerve agent VX, constitutes an important aspect for verifying the compliance to the CWC (Chemical Weapons Convention). This work devotes on the development of solid-phase extraction method using silica- and polymer-based SCX (strong cation-exchange) and MCX (mixed-mode strong cation-exchange) cartridges for N,N-dialkylaminoethane-2-ols and alkyl N,N-diethanolamines, from water. The extracted analytes were analyzed by GC-MS (gas chromatography-mass spectrometry) in the full scan and selected ion monitoring modes. The extraction efficiencies of SCX and MCX cartridges were compared, and results revealed that SCX performed better. Extraction parameters, such as loading capacity, extraction solvent, its volume, and washing solvent were optimized. Best recoveries were obtained using 2 mL methanol containing 10% NH(4)OH and limits of detection could be achieved up to 5 x 10(-3) microg mL(-1) in the selected ion monitoring mode and 0.01 microg mL(-1) in full scan mode. The method was successfully employed for the detection and identification of amino alcohol present in water sample sent by Organization for Prohibition of Chemical Weapons (OPCW) in the official proficiency tests. The method was also applied to extract the analytes from human plasma. The SCX cartridge showed good recoveries of amino alcohols from human plasma after protein precipitation.  相似文献   

4.
This paper describes a novel application of pristine and chemically modified multiwalled carbon nanotubes (MWCNTs) as the packing materials for the determination of different polyhalogenated organic pollutants, pentachlorophenol, 2,4,5-trichlorophenol, 3,3′,4,4′-tetrachlorobiphenyl and 2,2′,5,5′-tetrabromobiphenyl, from aqueous solution based on solid phase extraction. The modified MWCNTs were characterized using different techniques and the results revealed the successful modification of the MWCNTs with octadecyl amine and poly(ethylene glycol), separately. Factors that maybe influence the preconcentration efficiency, such as sample flow rate, adsorbent mass, sample pH and sample volume, were studied. Desorption of the target analytes was studied using different solvents and the results showed that acetone was the best solvent for all the analytes compared with methanol and hexane. All the results indicated that the proposed method could be used for the simultaneous determination of different pollutants in environmental water samples at trace levels.  相似文献   

5.
Efficient extraction of chemical warfare agents (CWAs) from water is essential before subjecting them to gas chromatographic and spectral analysis aiming towards verification of the Chemical Weapons Convention (CWC). It requires development of fast, reliable, simple and reproducible sample preparation of CWAs from water which is likely to be contaminated during deliberate or inadvertent spread of CWAs. This work describes development of a solid-phase extraction method using hydrophilic-lipophilic balance (HLB) cartridges for extraction of CWAs from water. The extraction efficiencies of HLB and C18 cartridges were compared and the results revealed that HLB sorbents performed better. Extracts were analyzed by gas chromatography-mass spectrometry. Extraction parameters, such as extraction solvent, its volume and rinsing solvent were optimized. Best recoveries of target analytes were obtained using 1mL methanol and limits of detection were achieved up to 0.05microg/mL with dichloromethane. Precision of the method was found to be less than 9.2% RSD.  相似文献   

6.
Selective extraction and enrichment of nerve agent degradation products has been achieved using zirconia based commercial solid-phase extraction cartridges. Target analytes were O-alkyl alkylphosphonic acids and alkylphosphonic acids, the environmental markers of nerve agents such as sarin, soman and VX. Critical extraction parameters such as modifier concentration, nature and volume of washing and eluting solvents were investigated. Amongst other anionic compounds, selectivity in extraction was observed for organophosphorus compounds. Recoveries of analytes were determined by GC-MS which ranged from 80% to 115%. Comparison of zirconia based solid-phase extraction method with anion-exchange solid-phase extraction revealed its selectivity towards phosphonic acids. The limits of detection (LOD) and limit of quantification (LOQ) with selected analytes were achieved down to 4.3 and 8.5 ng mL(-1), respectively, in selected ion monitoring mode.  相似文献   

7.
A simple, sensitive and selective solid phase microextraction with hollow fiber-supported multi-walled carbon nanotube functionalization reinforced sol–gel combined HPLC method was proposed for the determination of naproxen in tap, well and river water samples. In this method, functionalized multi-walled carbon nanotubes (MWCNTs) were prepared and held in pores of hollow fiber with sol–gel technology by immersion of polypropylene hollow fiber segment into the sol of the functionalized MWCNTs/silica composite and ultrasonically treated at room temperature. Effect of main parameters such as volume of donor phase, pH, extraction time, desorption time, type of desorption solvent, sample ionic strength and stirring rate were studied. Under optimum conditions, linearity was observed in the range of 0.03–500 ng/mL, with correlation coefficients of 0.997. The relative standard deviation for three replicate determinations of 50 ng/mL of naproxen was 4.3%. Limit of detection and pre-concentration factor were 0.008 ng/mL and 198, respectively. In order to check the applicability of the proposed method, it was used to determine trace levels of naproxen in different water samples.  相似文献   

8.
In this paper, solid‐phase extraction (SPE) in combination with dispersive liquid–liquid microextraction (DLLME) has been developed as a sample pretreatment method with high enrichment factors for the sensitive determination of amide herbicides in water samples. In SPE–DLLME, amide herbicides were adsorbed quantitatively from a large volume of aqueous samples (100 mL) onto a multiwalled carbon nanotube adsorbent (100 mg). After elution of the target compounds from the adsorbent with acetone, the DLLME technique was performed on the resulting solution. Finally, the analytes in the extraction solvent were determined by gas chromatography–mass spectrometry. Some important extraction parameters, such as flow rate of sample, breakthrough volume, sample pH, type and volume of the elution solvent, as well as salt addition, were studied and optimized in detail. Under optimum conditions, high enrichment factors ranging from 6593 to 7873 were achieved in less than 10 min. There was linearity over the range of 0.01–10 μg/L with relative standard deviations of 2.6–8.7%. The limits of detection ranged from 0.002 to 0.006 μg/L. The proposed method was used for the analysis of water samples, and satisfactory results were achieved.  相似文献   

9.
A procedure for the preconcentration of copper was described in this paper using multi-walled carbon nanotubes (MWCNTs) oxidized by potassium permanganate as the adsorbent for the enrichment of trace copper in water samples. Important parameters, such as the sample pH, the concentration and volume of eluent, sample flow rate and volume, and interference of coexisting ions, were investigated. The obtained results indicated that proposed method possessed an excellent analytical performance. The linear range, the detection limit, and precison (RSD) were 1-100 ng/mL (R2 = 0.9993), 0.32 ng/mL and 2.88%, respectively. The results showed that copper could be adsorbed quantitatively on the pretreated MWCNTs with potassium permanganate, and proposed method was very useful in the monitoring of copper in the environment.  相似文献   

10.
A flow injection solid-phase extraction preconcentration system using a multi-walled carbon nanotubes (MWCNTs) packed micro-column was developed for the determination of 16 polycyclic aromatic hydrocarbons (PAHs) in water by gas chromatography–mass spectrometry (GC–MS). The preconcentration of PAHs on the MWCNTs was carried out based on the adsorption retention of analytes by on-line introducing the sample into the micro-column system. Methanol was introduced to elute the retained analytes for GC–MS analysis using selected ion monitoring (SIM) mode. Important influence factors were studied in detail, such as sample acidity, sample flow rate, eluent flow rate and volume, dimensions of MWCNTs and amounts of packing material. Limits of detection of 16 PAHs for an extraction of 50 mL water sample were in the range of 0.001–0.15 μg L−1, and the precisions (RSD) were in the range of 4–14%. The optimized method was successfully applied to the determination of 16 PAHs in surface waters, with recoveries in the range of 72–93% for real spiked sample.  相似文献   

11.
A sensitive and selective preconcentration method using solid-phase extraction (SPE) disk, namely multiwalled carbon nanotubes (MWCNTs) disk, is proposed for the determination of atrazine and simazine in water samples. Atrazine and simazine were extracted on MWCNTs disk and then determined by gas chromatography–mass spectrometry (GC/MS). Several parameters on the enrichment factor of the analytes were investigated. The experimental results showed that it was possible to obtain quantitative analysis when the solution pH was 5 using 200 mL of validation solution containing 0.1 μg of triazines and 5 mL of acetone as an eluent. The maximum enrichment factors for atrazine and simazine were 3900 ± 250 and 4000 ± 110, respectively when 200 mL of sample solution volume was used. Relative standard deviations for seven determinations were 6.9% (atrazine) and 3.0% (simazine) under optimum conditions. The linear range of calibration curves were 0.1 to 1 ng mL− 1 for each analyte with good correlation coefficients. The detection limits (3S/N) were 2.5 and 5.0 pg mL− 1 for atrazine and simazine, respectively. The proposed method was successfully applied to the determination of atrazine and simazine in environmental water samples with high precision and accuracy.  相似文献   

12.
Xiao Q  Hu B  Yu C  Xia L  Jiang Z 《Talanta》2006,69(4):848-855
A single-drop microextraction (SDME) procedure was developed for the analysis of organophosphorus pesticides (OPPs) in water and fruit juice by gas chromatography (GC) with flame photometric detection (GC-FPD). The significant parameters affecting the SDME performance such as selection of microextraction solvent, solvent volume, extraction time, stirring rate, sample pH and temperature, and ionic strength were studied and optimized. Two types of SDME mode, static and cycle-flow SDME, were evaluated. The static SDME procedure provided more sensitive analysis of the target analytes. Therefore, static SDME with tributyl phosphate (TBP) as internal standard was selected for the real sample analysis. The limits of detection (LODs) in water for the six studied compounds were between 0.21 and 0.56 ng/mL with the relative standard deviations ranging from 1.7 to 10.0%. Linear response data was obtained in the concentration range of 0.5-50 ng/mL (except for dichlorvos 1.0-50 ng/mL) with correlation coefficients from 0.9995 to 0.9999. Environmental water sample collected from East Lake and fruit juice samples were successfully analyzed using the proposed method, but none of the analytes in both lake water and fruit juice were detected. The recoveries for the spiked water and juice samples were from 77.7 to 113.6%. Compared with the conventional methods, the proposed method enabled a rapid and simple determination of organophosphorus pesticides in water and fruit juice with minimal solvent consumption and a higher concentration capability.  相似文献   

13.
In this study, an extraction and preconcentration technique using solid-phase extraction (SPE) along with hollow fiber (HF) has been developed as an ultra-preconcentration technique for some triazole pesticides in aqueous samples. Triazole pesticides were employed as model compounds to assess the method and were monitored by gas chromatography-flame ionization detection (GC-FID). Initially, an aqueous solution of target analytes was passed through an RP-8 SPE cartridge and then the adsorbed analytes were eluted with μL amounts of toluene. The collected elute was slowly introduced into an HF that had one end blocked. This allowed precipitation inside the lumen and pores of the HF. Finally, the obtained HF was mounted on a home-made solid-phase microextraction syringe and entered into the GC injection port for thermal desorption-GC analysis. The effect of various experimental parameters including injection port temperature, desorption time, state of HF, washing solvent, elution solvent and its volume, sample volume, etc. were investigated for finding the optimum conditions. The calibration graphs were linear in the ranges of 2-1000 ng/mL (penconazole and hexaconazole), 5-1000 ng/mL (tebuconazole), 15-1000 ng/mL (triticonazole) and the detection limits (LODs) ranged from 0.6 to 4.5 ng/mL. The enhancement factors were in the range of 870-950. The relative standard deviations (RSD%) for five repeated experiments (C=250 ng/mL of each pesticide) varied from 4.5 to 8.7%. The relative recoveries obtained for analytes in grape juice samples, spiked with different levels of each pesticide, were in the range of 87-119%.  相似文献   

14.
Two low-volume solvent continuous extraction methods are applied to the extraction of paper matrices. In the methods reported here, a complex mixture of fluorescent whitening agents (FWAs) and azo dyes (AZOs) used in paper materials intended to come into contact with foodstuffs was extracted by using subcritical water extraction (SWE) and dynamic sonication-assisted solvent extraction (DSASE). Rationale for the work is based upon migration concerns of these groups of analytes from the packaging to the packaged items, thus compromising their subjective and/or objective quality. In SWE, sample was extracted in 21 min with 0.5 mL of water, whereas the DSASE method required 11 min and used 7 mL of water. DSASE was further developed by incorporating an organic modifier in order to change water polarity, thus improving extraction of moderately polar analytes. This way, modified-DSASE used a total organic volume of 0.9 mL which represents a reduction of 200 times in organic solvent consumption (200 mL versus approximately 1.0 mL) and 11 times in extraction time (2h versus 11 min) compared to the existing methods. SWE was able to extract only 9 out of 12 test analytes with average recoveries between 10 and 25% whereas modified-DSASE succeed in extracting all the target analytes with an average recovery of 89%. Complete discussion and explanation concerning these differences are provided in the text.  相似文献   

15.
The coextraction of acidic and basic compounds from different mediums is a significant concept in sample preparation. In this work, simultaneous extraction of acidic, basic, and neutral analytes in a single step was carried out for the first time. This procedure employed the dispersive solid‐phase microextraction of analytes with magnetic graphene oxide (graphene oxide/Fe3O4) sorbent followed by gas chromatography with flame ionization detection. After the adsorption of analytes by vortexing and decantation of the supernatant with a magnet, the sorbent was eluted with acetonitrile/methanol (2:1) mixture. The parameters affecting the extraction efficiency were optimized and obtained as follows: sorbent amount 60 mg, desorption time 1 min, extraction time 5 min, pH of the sample 7, sample volume 20 mL, and elution solvent volume 0.3 mL. Under the optimum conditions, linear dynamic ranges were achieved in the range of 0.5–4, 0.25–4, and 0.25–2 μg/mL and limits of detection were 0.341, 0.110, and 0.167 μg/mL for aniline, phenol, and naphthalene, respectively. The relative standard deviations were in the range of 3.3–5.7% in eight repeated extractions. Finally, the applicability of the method was evaluated by the extraction and determination of analytes in stream water and drinking water samples and satisfactory results were obtained.  相似文献   

16.
A simple, rapid, accurate and sensitive method using microextraction by packed sorbent (MEPS) followed by GC–MS has been pursued for the determination of organochlorine insecticide endosulfan isomers (α and β) and their metabolites (ether, lactone and sulfate). MEPS is a miniaturised version of SPE employing C18 packing material. It is very efficient technique as it employs as low as 10 μL of sample volume. The distinct feature of MEPS is the magnitude of the elution volume that could be directly injected to GC system. Various parameters such as extraction cycles, washing solvent, elution solvent, elution volume and pH, which influenced the MEPS performance, were tested and optimised. The calibration curves were obtained in the concentration range 1–500 ng/mL. The results showed a close correlation coefficient (R2 > 0.991) for all analytes in the calibration range studied. The LOD and LOQ obtained for GC–MS under selected ion monitoring acquisition are between 0.0038–0.01 and 0.0125–0.033 ng/mL, respectively. The developed method is applicable for the quantification of these compounds in tap water and commercial samples. This method has been shown to be selective as no interferences from endogenous substances were detected by analysis. This method not only decreases sample preparation time but is cheaper, eco‐friendly and easier to perform compared to traditional techniques.  相似文献   

17.
This paper introduced a novel test method for determination of the main demulsifier‐based pollutants in the produced water of oil wells, before draining to seawater. The type, concentration and distribution of diols depend on the demulsifier of interest; however, the main chemical species are the same. The novelty of this work is selective extraction and preconcentration of low chain diols in the produced water of oil fields. In this extraction method, dispersive solvent (1.2 mL, acetonitrile) containing extraction solvent (10.0 μL, carbon tetrachloride) was rapidly injected into the water sample containing analytes, and a cloudy solution was formed. After centrifugation (2 min at 3,000 rpm), these droplets were sedimented in the bottom of the conical test tube. Then 2.0 mL of sedimented phase containing preconcentrated analytes was injected into the gas chromatograph with flame ionization detector. The parameters affecting the extraction efficiency were evaluated and optimized. Factors such as the kind and volume of both extraction and disperser solvents, extraction and centrifugation times, pH and temperature, and salt effect were studied and optimized. The method exhibited enrichment factors and recoveries ranging from 39.0 to 44.4 and 78.9 to 92.2%, respectively, within very short extraction time. The linearity (and limit of detection) of the method ranged 4.0‐100.0 (2.0) ng/mL for 1,2‐ethandiol, 6.0‐80.0 (4.0) ng/mL for 1,3‐propandiol, 2.0‐90.0 (1.0) ng/mL ng/mL for 1,4‐butanediol, 5.0‐120.0 (2.0) ng/mL for 1,5‐pentandiol. The relative standard deviations (RSD) for the concentration of diols, 5.0 ng/mL in water by using the internal standard were in the range of 1.5–4.5% (n = 5) and without the internal standard was in the range of 2.6–9.0% (n = 5). It is concluded that this method is successful for determination of diols in produced water samples.  相似文献   

18.
Solid-phase extraction combined with dispersive liquid-liquid microextraction (SPE-DLLME) was applied for the extraction of six organophosphorous pesticides (OPPs) in water samples. The analytes considered in this study were determined by gas chromatography with mass spectrometry and included prophos, diazinon, chlorpyrifos methyl, methyl parathion, fenchlorphos and chlorpyrifos. Several extraction conditions (extraction solvent and elution/dispersion solvents nature, extraction solvent volume, elution solvent volume, water volume and sample volume) were tested for SPE-DLLME with these analytes and the best results were obtained using carbon tetrachloride as the extraction solvent and acetone as the elution/dispersion solvent. Calibration curves for the determination of OPPs in water samples were constructed in the concentration range of 10-100 ng/L. Limits of detection (LODs) ranged from 38 to 230 pg/L values that are below the maximum admissible level for drinking water (100 ng/L). Relative standard deviations (RSD) were between 8.6 and 10.4% for a fortification level of 100 ng/L. At the same fortification level, the relative recoveries (R.R.) of tap, well and irrigation water samples were in the range of 30.2-97.1%.  相似文献   

19.
Solid-phase extraction of soy isoflavones   总被引:3,自引:0,他引:3  
An automated method using solid-phase extraction (SPE) for the concentration and clean-up of soy isoflavone extracts is proposed in this work. Using a standardized sample (0.1 g of a freeze dried soybean extract/25 mL of water); eight SPE cartridges with a wide range of sorbents (C18, divinylbenzene and modified divinylbenzene) from different suppliers were evaluated and compared. A large variation on SPE cartridges performance was observed, especially regarding retention and breakthrough volume of isoflavones during sample load and washing steps. The most effective cartridges were the divinylbenzene based cartridges, especially Strata X (from Phenomenex) and HLB oasis (from Waters). Using Strata X cartridges, several extraction parameters, such as sample loading flow (5-15 mL min(-1)), extracting solvent volume (2-6 mL of methanol), pH of the extracting solvent and the necessity of drying the sorbent before elution, were evaluated to provide a fast, specific, quantitative and reproducible SPE method. The optimized method consists of conditioning the cartridge with 10 mL of methanol and 10 mL of water (10 mL min(-1)), loading 25 mL of the standardized extract onto the cartridges (5 mL min(-1)), washing the cartridge with 10 mL of water (10 mL min(-1)) and finally eluting with 4 mL of methanol (10 mL min(-1)). Mean isoflavones recovery was 99.37% and mean intra- and inter-day reproducibility was higher than 98%. The developed sample clean-up/concentration (6.25:1) method takes less than 10 min and can be used in the analysis of isoflavones from soy extracts.  相似文献   

20.
A simple and green reversed-phase ultrasonic assisted liquid?liquid microextraction method for determination of Cu, Cd, Ni, Pb and Zn in edible oils was developed. Detection was carried out by flame atomic absorption spectrometry. The influence of main parameters including ultrasonic time and temperature, disperser solvent, volume of extracting solvent and centrifuging time on the extraction efficiency of target analytes were investigated and optimized. In the proposed method, a few microliters of water (containing 3%, v/v, nitric acid) as extracting solvent was injected into the oil sample and mixture transferred to ultrasonic bath. Then, the mixture was centrifuged in order to accelerate in phase separation. Finally, the aqueous phase was removed and delivered to flame atomic absorption spectrometer. Calibration curves for all metals were linear in the range of 5?100 ng/mL. The limit of detections for Cu, Cd, Ni, Pb and Zn were 0.8, 0.3, 0.5, 1.5 and 0.5 ng/mL, respectively. Relative standard deviation (RSD) values were in the range of 0.6?1.9%. The recoveries were in the range of 95.2–101.2% with RSD values ranging from 0.8 to 1.9%. The proposed method was applied successfully for the determination of interested metals in commercial edible oils.  相似文献   

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