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1.
Dispersive liquid–liquid microextraction (DLLME) for extraction and preconcentration of phenoxyacetic acid herbicides in water samples is described. After adjusting the pH to 1.5, the sample was extracted in the presence of 10% w/v sodium chloride by injecting 1 mL acetone as disperser solvent containing 25 μL of chlorobenzene as extraction solvent. The effect of parameters, such as the nature and amount of extraction and disperser solvents, ionic strength of the sample, pH, temperature and extraction time were optimized. DLLME was followed by LC for the determination of 2,4-dichlorophenoxyacetic acid and 4-chloro-2-methyl phenoxyacetic acid. The method had good linearity and a wide linear dynamic range (0.5–750 μg L?1) with a detection limit of 0.16 μg L?1 for both the PAAs, making it suitable for their determination in water samples.  相似文献   

2.
In this work, a new method based on dispersive liquid–liquid microextraction (DLLME) preconcentration using tetrachloromethane (CCl4) as extraction solvent was proposed for the spectrophotometric determination of cadmium and copper in water and food samples. The influence factors relevant to DLLME, such as type and volume of extractant and disperser solvent, concentration of chelating reagents, pH, salt effect, were optimized. Under the optimal conditions, the limits of detection for cadmium and copper were 0.01 ng/L and 0.5 μg/L, with enhancement factors (EFs) of 3458 and 10, respectively. The tremendous contrast of EFs could come from the different maximum absorption wavelength caused by the different extraction acidity compared with some conventional works and the enhancement effect of acetone used as dilution solvent during the spectrophotometric determination. The proposed method was applied to the determination of water and food samples with satisfactory analytical results. The proposed method was simple, rapid, cost-efficient and sensitive, especially for the detection of cadmium.  相似文献   

3.
A novel method for the simultaneous determination of sulfonamides (SAs) in water samples has been developed by using dispersive liquid–liquid microextraction (DLLME) coupled with CE. Orthogonal and Box–Behnken designs were employed together to assist the optimization of DLLME parameters, including volumes of extraction and disperser solvents, ionic strength, extraction time, and centrifugation time and speed as variable factors. Under the optimum extraction and detection conditions, successful separation of the five SAs was achieved within 5 min, and excellent analytical performances were attained, such as good linear relationships (R>0.980) between peak area and concentration for each SA from 0.5 to 50 μg/mL, low limits of detection for the five SAs between 0.020 and 0.570 μg/mL and the intra‐day precisions of migration time below 0.80%. The method recoveries obtained at fortified 10 μg/mL for three water samples ranged from 53.6 to 94.0% with precisions of 1.23–5.60%. The proposed method proved highly sensitive and selective, rapid, convenient and cost‐effective, showing great potential for the simultaneous determination of SAs in water samples.  相似文献   

4.
Herein, an amino‐based silica‐coated nanomagnetic sorbent was applied for the effective extraction of two chlorophenoxyacetic acids (2‐methyl‐4‐chlorophenoxyacetic acid and 2,4‐dichlorophenoxyacetic acid) from various water samples. The sorbent was successfully synthesized and subsequently characterized by scanning electron microscopy, X‐ray diffraction, and Fourier‐transform infrared spectroscopy. The analytes were extracted by the sorbent mainly through ionic interactions. Once the extraction of analytes was completed, they were desorbed from the sorbent and detected by high‐performance liquid chromatography with ultraviolet detection. A number of factors affecting the extraction and desorption of the analytes were investigated in detail and the optimum conditions were established. Under the optimum conditions, the calibration curves were linear over the concentration range of 1–250, and based on a signal‐to‐noise ratio of 3, the method detection limits were determined to be 0.5 μg/L for both analytes. Additionally, a preconcentration factor of 314 was achieved for the analytes. The average relative recoveries obtained from the fortified water samples varied in the range of 91–108% with relative standard deviations of 2.9–8.3%. Finally, the method was determined to be robust and effective for environmental water analysis.  相似文献   

5.
Two microextraction techniques – liquid phase microextraction based on solidification of a floating organic drop (LPME‐SFO) and dispersive liquid–liquid microextraction combined with a solidification of a floating organic drop (DLLME‐SFO) – are explored for benzene, toluene, ethylbenzene and o‐xylene sampling and preconcentration. The investigation covers the effects of extraction solvent type, extraction and disperser solvents' volume, and the extraction time. For both techniques 1‐undecanol containing n‐heptane as internal standard was used as an extracting solvent. For DLLME‐SFO acetone was used as a disperser solvent. The calibration curves for both techniques and for all the analytes were linear up to 10 μg/mL, correlation coefficients were in the range 0.997–0.998, enrichment factors were from 87 for benzene to 290 for o‐xylene, detection limits were from 0.31 and 0.35 μg/L for benzene to 0.15 and 0.10 μg/L for o‐xylene for LPME‐SFO and DLLME‐SFO, respectively. Repeatabilities of the results were acceptable with RSDs up to 12%. Being comparable with LPME‐SFO in the analytical characteristics, DLLME‐SFO is superior to LPME‐SFO in the extraction time. A possibility to apply the proposed techniques for volatile aromatic hydrocarbons determination in tap water and snow was demonstrated.  相似文献   

6.
Solid‐phase extraction coupled with dispersive liquid–liquid microextraction was developed as an ultra‐preconcentration method for the determination of four organophosphorus pesticides (isocarbophos, parathion‐methyl, triazophos and fenitrothion) in water samples. The analytes considered in this study were rapidly extracted and concentrated from large volumes of aqueous solutions (100 mL) by solid‐phase extraction coupled with dispersive liquid–liquid microextraction and then analyzed using high performance liquid chromatography. Experimental variables including type and volume of elution solvent, volume and flow rate of sample solution, salt concentration, type and volume of extraction solvent and sample solution pH were investigated for the solid‐phase extraction coupled with dispersive liquid–liquid microextraction with these analytes, and the best results were obtained using methanol as eluent and ethylene chloride as extraction solvent. Under the optimal conditions, an exhaustive extraction for four analytes (recoveries >86.9%) and high enrichment factors were attained. The limits of detection were between 0.021 and 0.15 μg/L. The relative standard deviations for 0.5 μg/L of the pesticides in water were in the range of 1.9–6.8% (n = 5). The proposed strategy offered the advantages of simple operation, high enrichment factor and sensitivity and was successfully applied to the determination of four organophosphorus pesticides in water samples.  相似文献   

7.
A novel dispersive liquid–liquid microextraction (DLLME) method followed by HPLC analysis, termed sequential DLLME, was developed for the preconcentration and determination of aryloxyphenoxy‐propionate herbicides (i.e. haloxyfop‐R‐methyl, cyhalofop‐butyl, fenoxaprop‐P‐ethyl, and fluazifop‐P‐butyl) in aqueous samples. The method is based on the combination of ultrasound‐assisted DLLME with in situ ionic liquid (IL) DLLME into one extraction procedure and achieved better performance than widely used DLLME procedures. Chlorobenzene was used as the extraction solvent during the first extraction. Hydrophilic IL 1‐octyl‐3‐methylimidazolium chloride was used as a dispersive solvent during the first extraction and as an extraction solvent during the second extraction after an in situ chloride exchange by bis[(trifluoromethane)sulfonyl]imide. Several experimental parameters affecting the extraction efficiency were studied and optimized with the design of experiments using MINITAB® 16 software. Under the optimized conditions, the extractions resulted in analyte recoveries of 78–91%. The correlation coefficients of the calibration curves ranged from 0.9994 to 0.9997 at concentrations of 10–300, 15–300, and 20–300 μg L?1. The relative SDs (n = 5) ranged from 2.9 to 5.4%. The LODs for the four herbicides were between 1.50 and 6.12 μg L?1.  相似文献   

8.
A simple, rapid, and efficient method, vortex‐assisted extraction followed by dispersive liquid–liquid microextraction (DLLME) has been developed for the extraction of polycyclic aromatic hydrocarbons (PAHs) in sediment samples prior to analysis by high performance liquid chromatography fluorescence detection. Acetonitrile was used as collecting solvent for the extraction of PAHs from sediment by vortex‐assisted extraction. In DLLME, PAHs were rapidly transferred from acetonitrile to dichloromethane. Under the optimum conditions, the method yields a linear calibration curve in the concentration range from 10 to 2100 ng g?1 for fluorene, anthracene, chrysene, benzo[k]fluoranthene, and benzo[a]pyrene, and 20 to 2100 ng g?1 for other target analytes. Coefficients of determinations ranged from 0.9986 to 0.9994. The limits of detection, based on signal‐to‐noise ratio of three, ranged from 2.3 to 6.8 ng g?1. Reproducibility and recoveries was assessed by extracting a series of six independent sediment samples, which were spiked with different concentration levels. Finally, the proposed method was successfully applied in analyses of real nature sediment samples. The proposed method extended and improved the application of DLLME to solid samples, which greatly shorten the extraction time and simplified the extraction process.  相似文献   

9.
Dispersive liquid?Cliquid microextraction (DLLME) has been proposed for the extraction and preconcentration of 12 carbamate pesticides in juice samples, followed by their determination by micellar electrokinetic chromatography with diode-array detection. To improve sensitivity, an on-capillary sample concentration method based on sweeping has been developed. Also, separations were performed in an extended light path fused-silica capillary; the separation buffer consisted of 100?mM borate and 50?mM SDS (pH?9.0) with 5% acetonitrile. Samples were introduced by hydrodynamic injection, dissolved in the separation buffer, but free of micelles. Several parameters of the DLLME procedure (such as type and volume of extraction and dispersive solvents, pH, salt addition, and extraction time) were optimized. Recoveries obtained for fortified juice samples (banana, pineapple, and tomato) at three different concentration levels, ranged from 78% to 105%, with relative standard deviations lower than 9%. The limits of detection ranged from 1 to 7???g l?1. Moreover, the method is fast, simple, and environmentally friendly.  相似文献   

10.
SPE joined with dispersive liquid–liquid microextraction based on solidification of floating organic drop (DLLME‐SFO) as a novel technique combined with GC with electron‐capture detection has been developed as a preconcentration technique for the determination of organochlorine pesticides (OCPs) in water samples. Aqueous samples were loaded onto multiwalled carbon nanotubes as sorbent. After the elution of the desired compounds from the sorbent by using acetone, the DLLME‐SFO technique was performed on the obtained solution. Variables affecting the performance of both steps such as sample solution flow rate, breakthrough volume, type and volume of the elution, type and volume of extraction solvent and salt addition were studied and optimized. The new method provided an ultra enrichment factor (8280–28221) for nine OCPs. The calibration curves were linear in the range of 0.5–1000 ng/L, and the LODs ranged from 0.1–0.39 ng/L. The RSD, for 0.01 μg/L of OCPs, was in the range of 1.39–13.50% (n = 7). The recoveries of method in water samples were 70–113%.  相似文献   

11.
The applicability of an ionic liquid‐based cationic surfactant 1‐dodecyl‐3‐methyl‐imidazolium tetrafluoroborate (C12MImBF4) as pseudostationary phase in MEKC has been evaluated for the analysis of 11 carbamate pesticides (promecarb, carbofuran, metolcarb, fenobucarb, aldicarb, propoxur, asulam, benomyl, carbendazim, ethiofencarb, isoprocarb) in juice samples. Under optimum conditions (separation buffer, 35 mM NaHCO3 and 20 mM C12MImBF4, pH 9.0; capillary temperature 25°C; voltage –22 kV) the analysis was carried out in less than 12 min, using hydrodynamic injection (50 mbar for 7.5 s) and detection at 200 nm. For the extraction of these CRBs from juice samples, a dispersive liquid–liquid microextraction (DLLME) procedure has been proposed, by optimization of variables affecting the efficiency of the extraction. Following this treatment, sample throughput was approximately 12 samples per hour, obtaining a preconcentration factor of 20. Matrix‐matched calibration curves were established using tomato juice as representative matrix (from 5 to 250 μg/L for CBZ, BY, PX, CF, FEN, ETH, ISP, and 25–250 μg/L for ASL, ALD, PRC, MTL), obtaining quantification limits ranging from 1 to 18 μg/L and recoveries from 70 to 96%, with RSDs lower than 9%.  相似文献   

12.
In this work, the potential of a symmetric dialkyl‐substituted ionic liquid (IL), 1,3‐dipenthylimidazolium hexafluorophosphate ([PPIm][PF6]), as extraction solvent in dispersive liquid–liquid microextraction (DLLME) has been studied for the analysis of a group of three natural (estriol, 17β‐estradiol, and 17α‐estradiol) and four synthetic (17α‐ethynylestradiol, diethylstibestrol, dienestrol, and hexestrol) estrogenic compounds as well as one mycotoxin with estrogenic activity (zearalenone) in different types of water samples (Milli‐Q, mineral, and wastewater). Separation, determination, and quantification were developed by HPLC‐DAD and a fluorescence detector (FD) connected in series. Factors influencing the IL‐DLLME procedure (sample pH, amount of IL, type and volume of disperser solvent, ionic strength, and assistance of vortex agitation) were investigated and optimized by means of a step‐by‐step approach. Once the optimum extraction conditions were established (10 mL of water at pH 8, 60 mg of [PPIm][PF6], 500 μL of ACN as disperser solvent and vortex agitation for 1 min), the calibration curves of the whole method (IL‐DLLME‐HPLC‐DAD/FD) were obtained and precision and accuracy were evaluated. It was demonstrated that the developed methodology was repeatable, accurate, and selective with limits of detection in the 0.30–0.57 μg/L and 13.8–37.1 μg/L range for FD and DAD, respectively. Relative recovery values were higher than 85% for the different types of water samples and the Student's t test demonstrated that there were not significant differences between the added and the found concentration.  相似文献   

13.
A dispersive liquid-liquid microextraction (DLLME) method using in situ halide exchange reaction to form ionic liquid (IL) extraction phase was developed to determine four insecticides (i.e. methoxyfenozide, tetrachlorvinphos, thiamethoxam, and diafenthiuron) in water samples. The preconcentration procedure, followed by high-performance liquid chromatography and variable wavelength detectors (VWD), enabled the formation of the immiscible IL extraction phase; the insecticides were transferred into the IL phase simultaneously, which enhanced the efficiency and sufficiency, greatly shortening the operation time. The experimental parameters affecting the extraction efficiency including volume of extraction IL, extraction and centrifugation times, volume of the sample solution and exchanging reagent, and addition of organic solvent and salt were investigated and optimized. Under optimized conditions, the extractions yielded recoveries of the target analytes from 82 to 102%. The calibration curves were linear, and the correlation coefficient ranged from 0.9990 to 0.9999 under the concentration levels of 5-200 μg/L. The relative standard deviation (n=6) was 2.9-4.6%. The limits of detection (LODs) for the four insecticides were between 0.98 and 2.54 μg/L.  相似文献   

14.
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   

15.
A zirconium(IV)‐based metal–organic framework material (MOF‐808) has been synthesized in a simple way and used for the extraction of phenoxyacetic acids in complex samples. The material has good thermal and chemical stability, large specific surface area (905.36 m²/g), and high pore size (22.18 Å). Besides, it contains a large amount of Zr‐O groups, easy‐to‐form Zr‐O‐H bond with carboxyl groups of phenoxyacetic acids, and possesses biphenyl skeleton structure, easy to interact with compounds through π‐π and hydrophobic interactions. These characteristics make the material very suitable for the extraction of certain compounds with a high extraction efficiency and excellent selectivity. The extraction conditions were optimized, and then an analytical method was successfully established and applied for analysis of actual samples. The solid‐phase extraction method based on prepared material had a wide linear range of 0.2–250 μg/L and a low detection limit of 0.1–0.5 μg/L for four phenoxyacetic acid compounds including 2,4‐dichlorophenoxyacetic acid, 2‐(2,4‐dichlorophenoxy) propionic acid, 4‐chlorophenoxyacetic acid, and dicamba. The relative standard deviations of intra‐ and interday precision were 1.8–3.8 and 4.3–6.9%, and the recoveries after spiking were between 77.1 and 109.3%. The results showed that the material is a desired substituent for the extraction of compounds with benzene ring structure containing carboxyl groups.  相似文献   

16.
Solid‐phase extraction (SPE) in tandem with dispersive liquid–liquid microextraction (DLLME) has been developed for the determination of mononitrotoluenes (MNTs) in several aquatic samples using gas chromatography‐flame ionization (GC‐FID) detection system. In the hyphenated SPE‐DLLME, initially MNTs were extracted from a large volume of aqueous samples (100 mL) into a 500‐mg octadecyl silane (C18) sorbent. After the elution of analytes from the sorbent with acetonitrile, the obtained solution was put under the DLLME procedure, so that the extra preconcentration factors could be achieved. The parameters influencing the extraction efficiency such as breakthrough volume, type and volume of the elution solvent (disperser solvent) and extracting solvent, as well as the salt addition, were studied and optimized. The calibration curves were linear in the range of 0.5–500 μg/L and the limit of detection for all analytes was found to be 0.2 μg/L. The relative standard deviations (for 0.75 μg/L of MNTs) without internal standard varied from 2.0 to 6.4% (n=5). The relative recoveries of the well, river and sea water samples, spiked at the concentration level of 0.75 μg/L of the analytes, were in the range of 85–118%.  相似文献   

17.
A novel preconcentration/separation approach, which online combined CZE with CD‐modified MEKC, was developed for simultaneous enhancing resolving power and detection sensitivity. CZE with cation‐selective exhaustive injection and transient ITP preconcentration was used as the first dimension, from which the effluent fractions were further analyzed by CD‐modified MEKC acting as the second dimension. As the key to successful integration of CZE with MEKC, a new interface was designed and electroaccumulation focusing strategy was employed to avoid analyte band diffusion at the interface. The comprehensive 2‐D system was successfully established with only one high voltage and four electrodes. The grouping of two orthogonal separation techniques, together with analytes preconcentration techniques, significantly enhanced resolution and sensitivity for 2‐D separation of cationic compounds. The resulting electrophoregram was quite different from that of either single CZE or MEKC. Up to 14 000‐ to 35 000‐fold improvement in sensitivity was obtained relative to conventional electrokinetic injection method. The limits of detection (S/N=3) were in the range of 0.03–0.1 μg/L. The number of theoretical plates was in the range of 103 000–184 000. This method was successfully applied to the analysis of trace cationic cardiovascular drugs in wastewater.  相似文献   

18.
A new, simple and cheap dispersive liquid–liquid microextraction (DLLME) procedure was optimized for the preconcentration of trace amounts of Ni(II) as a prior step to its determination by flame atomic absorption spectrometry (FAAS). It is based on the microextraction of nickel, where appropriate amounts of the extraction solvent (CHCl3), disperser solvent (ethanol) and chelating agent, name 5‐[(Z)‐isoxazol‐3‐yl‐diazenyl]‐2‐methyl‐quinolin‐8‐ol (MMD), were firstly synthesized/characterized and used. Various parameters that affect the extraction procedure such as pH, centrifugation rate and time, the chelating agent (MMD) concentration and sampling volume on the recovery of Ni(II) were investigated. The preconcentration of a 20 ml sample solution was thus enhanced by a factor of 80. The resulting calibration graph was linear in the range of 0.24–10 mg L−1 with a correlation coefficient of 0.9998. The limit of detection (3 s/b) obtained under optimal conditions was 1.00 μg L−1. The relative standard deviation for certified reference material determinations was 1.2%. The accuracy of the method was verified by the determination of Ni(II) in the certified reference material of wastewater (Waste water CWW TMD). The proposed procedure was successfully applied to the determination of Ni(II) in some fake jewelry and cosmetics samples.  相似文献   

19.
An on‐line, fast, simple, selective, and sensitive method has been developed for the determination of three herbicides belonging to the following families: triazines (atrazine), chloroacetamide (alachlor), and phenoxy (2,4‐dichlorophenoxyacetic acid) in water samples. The method involves an in‐syringe magnetic stirring‐assisted dispersive liquid–liquid microextraction along with simultaneous silylation prior to their determination by gas chromatography with mass spectrometry. Extraction, derivatization, and preconcentration have been simultaneously performed using acetone as dispersive solvent, N‐methyl‐Ntert‐butyldimethylsilyltrifluoroacetamide as derivatization agent and trichloroethylene as extraction solvent. After stirring for 180 s, the sedimented phase was transferred to a rotary micro‐volume injection valve (3 μL) and introduced by an air stream into gas chromatograph with mass spectrometry detector. Recovery and enrichment factors were 87.2–111.2% and 7.4–10.4, respectively. Relative standard deviations were in the ranges of 6.6–7.4 for intraday and 9.2–9.6 for interday precision. The detection limits were in the range of 0.045–0.03 μg/L, and good linearity was observed up to 200 μg/L, with R2 ranging between 0.9905 and 0.9964. The developed method was satisfactorily applied to assess the occurrence of the studied herbicides in groundwater samples. The recovery test was also performed with values between 77 and 117%.  相似文献   

20.
A dispersive liquid–liquid microextraction (DLLME) method combined with solvolysis reaction for extraction of the carbamate fungicide benomyl as carbendazim from water samples is described. The method is based on the extraction of benomyl from acidified sample solution and its conversion into carbendazim via solvolysis reaction with DMF as organic solvent. The proposed DLLME method was followed by HPLC with fluorimetric detection for determination of benomyl. The proposed method has good linearity (0.998) with wide linear dynamic range (0.01–25 mg/L) and low detection limit (0.0033 mg/L), making it suitable for benomyl determination in water samples.  相似文献   

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