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1.
A new simple and rapid dispersive liquid–liquid microextraction method has been developed for the extraction and analysis of organochlorine pesticides (OCPs) in water samples. The method is based on the solidification of a floating organic drop (DLLME-SFO) and is combined with gas chromatography/electron capture detection (GC/ECD). Very little solvent is required in this method. The disperser solvent (200 μL acetonitrile) containing 10 μL hexadecane (HEX) is rapidly injected by a syringe into the 5.0 mL water sample. After centrifugation, the fine HEX droplets (6 ± 0.5 μL) float at the top of the screw-cap test tube. The test tube is then cooled in an ice bath. After 5 min, the HEX solvent solidifies and is then transferred into a conical vial, where it melts quickly at room temperature, and 1 μL of it is injected into a gas chromatograph for analysis. Under optimum conditions, the enrichment factors and extraction recoveries are high and range between 37–872 and 82.9–102.5%, respectively. The linear range is wide (0.025–20 μg L−1), and the limits of detection are between 0.011 and 0.11 μg L−1 for most of the analytes. The relative standard deviation (RSD) for 1 μg L−1 of OCPs in water was in the range of 5.8–8.8%. The performance of the method was gauged by analyzing samples of lake and tap water.  相似文献   

2.
A novel ultrasound-assisted surfactant-enhanced emulsification microextraction (UASEME) coupled with high performance liquid chromatography-diode array detection has been developed for the extraction and determination of six carbamate pesticides (metolcarb, carbofuran, carbaryl, pirimicarb, isoprocarb and diethofencarb) in water samples. In the UASEME technique, Tween 20 was used as emulsifier, and chlorobenzene and chloroform were used as dual extraction solvent without using any organic dispersive solvent that is normally required in the previously described common dispersive liquid–liquid microextraction method. Parameters that affect the extraction efficiency, such as the kind and volume of the extraction solvent, the type and concentration of the surfactant, ultrasound emulsification time and salt addition, were investigated and optimized for the method. Under the optimum conditions, the enrichment factors were in the range between 170 and 246. The limits of detection of the method were 0.1–0.3 ng mL−1 and the limits of quantification were between 0.3 and 0.9 ng mL−1, depending on the compounds. The linearity of the method was obtained in the range of 0.3–200 ng mL−1 for metolcarb, carbaryl, pirimicarb, and diethofencarb, 0.6–200 ng mL−1 for carbofuran, and 0.9–200 ng mL−1 for isoprocarb, with the correlation coefficients (r) ranging from 0.9982 to 0.9998. The relative standard deviations varied from 3.2 to 4.8% (n = 5). The recoveries of the method for the six carbamates from water samples at spiking levels of 1.0, 10.0, 50.0 and 100.0 ng mL−1 were ranged from 81.0 to 97.5%. The proposed UASEME technique has demonstrated to be simple, practical and environmentally friendly for the determination of carbamates residues in river, reservoir and well water samples.  相似文献   

3.
A simple and efficient liquid-phase microextraction (LPME) in conjunction with gas chromatography-electron capture detector (GC-ECD) has been developed for extraction and determination of 11 organochlorine pesticides (OCPs) from water samples. In this technique a microdrop of 1-dodecanol containing pentachloronitrobenzene (internal standard) is delivered to the surface of an aqueous sample while being agitated by a stirring bar in the bulk of solution. Following completion of extraction, the sample vial was cooled by putting it into an ice bath for 5 min. Finally 2 μL of the drop was injected into the GC for analysis. Factors relevant to the extraction efficiency were studied and optimized. Under the optimized extraction conditions (extraction solvent: 1-dodecanol; extraction temperature: 65 °C; sodium chloride concentration: 0.25 M; microdrop and sample volumes: 8 μL and 20 mL respectively; the stirring rate: 750 rpm and the extraction time: 30 min), figures of merit of the proposed method were evaluated. The detection limits of the method were in the range of 7-19 ng L−1 and the RSD% for analysis of 2 μg L−1 of OCPs was below 7.2% (n = 5). A good linearity (r2 ≥ 0.993) and a relatively broad dynamic linear range (25-2000 ng L−1) were obtained. After 30 min of extraction, preconcentration factors were in the range of 708-1337 for different organochlorine pesticides and the relative errors ranged from −10.1 to 10.9%. Finally the proposed method was successfully utilized for preconcentration and determination of OCPs in different real samples.  相似文献   

4.
In this study, the organochlorine pesticides (OCPs) levels in lake and tap water samples were determined by a dispersive liquid-liquid microextraction method using a low-density organic solvent and an improved solvent collection system (DLLME-ISCS). This method used a very small volume of a solvent of low toxicity (11 μL of 1-nonanol and 400 μL of methanol) to extract OCPs from 10 mL water samples prior to the analysis by GC. After centrifugation in the dispersive liquid-liquid microextraction, there was a liquid organic drop floating between the water surface and the glass wall of the centrifuge tube. The liquid organic drop (with some water phase) was transferred into a microtube (3 mm×15 mm) with a syringe. The organic and aqueous phases were separated in the microtube immediately. Then, 1 μL of the organic solvent (which was in the upper portion of liquid in the microtube) was easily collected by a syringe and injected into the GC-ECD system for the analysis. Under optimum conditions, the linear range of this method was 5-5000 ng/L for most of the analytes. The correlation coefficient was higher than 0.997. Enrichment factors ranged from 1309 to 3629. The relative recoveries ranged from 73 to 119% for lake water samples. The LODs of the method ranged from 0.7 to 9.4 ng/L. The precision of the method ranged from 1.0 to 10.8% for lake water.  相似文献   

5.
A solid-phase microextraction (SPME) procedure using two commercial fibers coupled with high-performance liquid chromatography (HPLC) is presented for the extraction and determination of organochlorine pesticides in water samples. We have evaluated the extraction efficiency of this kind of compound using two different fibers: 60-μm polydimethylsiloxane–divinylbenzene (PDMS-DVB) and Carbowax/TPR-100 (CW/TPR). Parameters involved in the extraction and desorption procedures (e.g. extraction time, ionic strength, extraction temperature, desorption and soaking time) were studied and optimized to achieve the maximum efficiency. Results indicate that both PDMS-DVB and CW/TPR fibers are suitable for the extraction of this type of compound, and a simple calibration curve method based on simple aqueous standards can be used. All the correlation coefficients were better than 0.9950, and the RSDs ranged from 7% to 13% for 60-μm PDMS-DVB fiber and from 3% to 10% for CW/TPR fiber. Optimized procedures were applied to the determination of a mixture of six organochlorine pesticides in environmental liquid samples (sea, sewage and ground waters), employing HPLC with UV-diode array detector.  相似文献   

6.
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   

7.
A simple, rapid, efficient, and environmentally friendly method for the determination of some triazine herbicides (simazine, atrazine, prometone, ametryn and prometryne) in water samples was developed by ultrasound-assisted emulsification microextraction (USAEME) coupled with high-performance liquid chromatography-diode array detection (HPLC-DAD). The main parameters that affect the extraction efficiencies, such as the kind and volume of the extraction solvent, ultrasound emulsification time and salt addition, were investigated and optimized. Under the optimum conditions, the method was sensitive and showed a good linearity within a range of 0.5 to 200?ngm?L?1 for simazine, atrazine, prometone, ametryn and prometryne, with the correlation coefficients (r) varying from 0.9993 to 0.9998. High enrichment factors were obtained ranging from 148 to 225. The limits of detection (LODs) were in the range between 0.06 and 0.1?ngm?L?1 and the limits of quantification (LOQs) were in the range between 0.2 and 0.3?ngm?L?1. The recoveries of the analytes from water samples at spiking levels of 5.0 and 50.0?ngm?L?1 were ranged from 82.4% to 107.0%. The relative standard deviations (RSDs) varied from 3.0% to 4.6%. The results demonstrated that the USAEME-HPLC-DAD method was an ef?cient pretreatment and enrichment procedure for the determination of triazine pesticides in real water samples.  相似文献   

8.
A novel ultrasound-assisted surfactant-enhanced emulsification microextraction (UASEME) technique has been proposed by using low-density extraction solvents. In the proposed technique, Tween 80 and cyclohexane were injected into 5-mL glass test tubes with conical bottoms, containing 5.00 mL of a water sample that was located inside the ultrasonic bath. When the extraction process was finished, the glass test tube was sealed with a rubber plug and then placed upside down in a centrifuge. The finely dispersed droplets of cyclohexane collected at the conical bottom of test tube because the density of cyclohexane is less than of water, and the PAHs were concentrated in the cyclohexane. Next, 5 μL of the cyclohexane that collected at the conical bottom was removed using a 10-μL microsyringe and injected into high performance liquid chromatography coupled with fluorescence detection (HPLC-FLD) for analysis. The proposed method avoided the use of chlorinated solvents, which have been widely used as extraction solvents in a normal UASEME assay. Parameters that affected the extraction efficiency, such as the type and volume of the extraction solvent, the type and concentration of the surfactant, and the ultrasound emulsification time and salt addition, were investigated and optimised for the method. Under the optimum conditions, the enrichment factors ranged between 90 and 247. The limits of detection of the method were 0.6-62.5 ng L(-1). Good recoveries and repeatability of the method for the eleven PAHs were also obtained. The proposed UASEME technique has been demonstrated to be simple, practical and environmentally friendly for the determination of PAH residues in real water samples.  相似文献   

9.
A rapid and simple dispersive liquid-liquid microextraction (DLLME) has been developed to preconcentrate eighteen organochlorine pesticides (OCPs) from water samples prior to analysis by gas chromatography-mass spectrometry (GC-MS). The studied variables were extraction solvent type and volume, disperser solvent type and volume, aqueous sample volume and temperature. The optimum experimental conditions of the proposed DLLME method were: a mixture of 10 μL tetrachloroethylene (extraction solvent) and 1 mL acetone (disperser solvent) exposed for 30 s to 10 mL of the aqueous sample at room temperature (20 °C). Centrifugation of cloudy solution was carried out at 2300 rpm for 3 min to allow phases separation. Finally, 2 μL of extractant was recovered and injected into the GC-MS instrument. Under the optimum conditions, the enrichment factors ranged between 46 and 316. The calculated calibration curves gave a high-level linearity for all target analytes with correlation coefficients ranging between 0.9967 and 0.9999. The repeatability of the proposed method, expressed as relative standard deviation, varied between 5% and 15% (n = 8), and the detection limits were in the range of 1-25 ng L−1. The LOD values obtained are able to detect these OCPs in aqueous matrices as required by EPA methods 525.2 and 625. Analysis of spiked real water samples revealed that the matrix had no effect on extraction for river, surface and tap waters; however, urban wastewater sample shown a little effect for five out of eighteen analytes.  相似文献   

10.
In this study, a novel graphene nanosheets (GNSs) coated solid phase microextraction (SPME) fiber was prepared by immobilizing microwave synthesized GNSs on a stainless steel wire. Microwave synthesized GNSs were verified by X-ray diffraction, field emission-scanning electron microscopy (FE-SEM) and transmission electron microscope (TEM). GNS-SPME fiber was characterized using FE-SEM and the results showed the GNS coating was homogeneous, porous, and highly adherent to the surface of the stainless steel fiber. The performance and feasibility of the GNS-SPME fiber was evaluated under one-step microwave assisted (MA) headspace (HS) SPME followed by gas chromatography with electron capture detection for five organochlorine pesticides (OCPs) in aqueous samples. Parameters influencing the extraction efficiency of MA-HS-GNS-SPME such as microwave irradiation power and time, pH, ionic strength, and desorption conditions were thoroughly examined. Under the optimized conditions, detection limits for the OCPs varied between 0.16 and 0.93 ng L(-1) and linear ranges varied between 1 and 1500 n gL(-1), with correlation coefficients ranging from 0.9984 to 0.9998, and RSDs in the range of 3.6-15.8% (n=5). In comparison with the commercial 100 μm polydimethylsiloxane fiber, the GNS coated fiber showed better extraction efficiency, higher mechanical and thermal stability (up to 290°C), longer life span (over 250 times), and lower production cost. The method was successfully applied to the analysis of real water samples with recoveries ranged between 80.1 and 101.1% for river water samples. The results demonstrated that the developed MA-HS-GNS-SPME method was a simple, rapid, efficient pretreatment and environmentally friendly procedure for the analysis of OCPs in aqueous samples.  相似文献   

11.
Microwave assisted micellar extraction (MAME) coupled with solid phase microextraction (SPME) and HPLC-UV determination have been used for the determination of five organochlorine pesticides from agricultural soil samples. A non-ionic surfactant, Polyoxyethlylene 10 Lauryl Ether was used, and the different variables for the optimization of MAME and SPME procedures were studied. This method was applied successfully to the determination of these pesticides in several kinds of agricultural soil samples with different characteristics. Most of the compounds studied can be recovered in good yields with R.S.D. lower than 9% and detection limit ranged between 56-96 ng g−1 for the pesticides studied.  相似文献   

12.
In this work, a simple, practical and environmentally friendly sample pre-treatment method, ultrasound-assisted surfactant-enhanced emulsification microextraction coupled with high performance liquid chromatography–diode array detector/electrospray ionisation mass spectrometry, was developed to determine diethofencarb and pyrimethanil residues in water and fruit juice samples. Tween 80 was used as an emulsifier and carbon tetrachloride was chosen as the extraction solvent, and no dispersive organic solvent was needed, which is typically required in common dispersive liquid–liquid microextraction methods. Several variables, such as the type and volume of extraction solvent and surfactant, extraction temperature and ultrasound extraction time were investigated and optimised. Under optimal conditions, the enrichment factors were 265 and 253 for diethofencarb and pyrimethanil, respectively. The limits of detection (LODs), calculated as three times the signal-to-noise ratio (S/N), were 0.01 μg L−1 for both diethofencarb and pyrimethanil. The linearity of the method was obtained in the range of 0.05–2000 μg L−1, with correlation coefficients of 0.9994–0.9998. The water (at fortified levels of 0.1 and 1.0 μg L−1) and fruit juice samples (at fortified levels of 0.1 and 1.0 μg L−1) were successfully analysed using the proposed method, and the relative recoveries were in the range of 88–114%, 93–111%, 86–117% and 94–101%, respectively.  相似文献   

13.
Dispersive liquid-liquid microextraction (DLLME) combined with gas chromatography and mass spectrometry (GC-MS) was applied to the determination of six organophosphorous pesticides (OPPs) in water samples. The analytes included in this study were prophos, diazinon, chlorpyrifos methyl, methyl parathion, fenchlorphos and chlorpyrifos. Several extraction and dispersion solvents were tested for dispersive liquid-liquid microextraction of these analytes and the best results were obtained using chloroform as extraction solvent and 2-propanol as dispersion solvent. Calibration curves of the analytes in water samples were constructed in the concentration range from 100 to 1100 ng/L for prophos, diazinon and methyl parathion and in the range from 100 to 1000 ng/L for chlorpyrifos methyl, fenchlorphos and chlorpyrifos. Limits of detection (LODs) were in the range of 1.5-9.1 ng/L and limits of quantification (LOQs) were in the range of 5.1-30.3 ng/L, below the maximum admissible level for drinking water. Relative standard deviations (RSDs) were between 6.5 and 10.1% in the concentration range of 100-1000 ng/L. The relative recoveries (%RRs) of tap, well and irrigation water samples fortified at 800 ng/L were in the range of 46.1-129.4%, with a larger matrix effect being detected in tap water.  相似文献   

14.
A simple, rapid, efficient, and environmentally friendly pretreatment based on a low‐density solvent based dispersive liquid–liquid microextraction was developed for determining trace levels of 17 organochlorine pesticides in snow. The parameters affecting the extraction efficiency, such as the type and volume of the extraction and dispersive solvents, extraction time, and salt content, were optimized. The optimized conditions yielded a good performance, with enrichment factors ranging from 271 to 474 and recoveries ranging from 71.4 to 114.5% and relative standard deviations between 1.6 and 14.8%. The detection limits, calculated as three times the signal‐to‐noise ratio, ranged from 0.02 to 0.11 μg/L. The validated method was used to successfully analyze 17 analytes in snow water samples, overcoming the drawbacks of some existing low‐density solvent liquid microextraction methods, which require special devices, large volumes of organic solvents, or complicated operation procedures.  相似文献   

15.
A procedure involving the simultaneous performance of liquid–liquid microextraction and polypropylene microporous membrane solid-phase extraction was carried out. The applicability of the proposed procedure was evaluated through extraction of several organochlorine pesticides from river water, tomato and strawberry samples. The parameters affecting the extraction efficiency were optimized by multivariable designs, and the analytical features were estimated. Under optimized conditions, analytes were concentrated onto 1.5 cm long microporous membranes placed directly into the sample containing 15 mL of water with 20 μL of 1-octanol. The best extraction conditions were achieved at 59 °C, with 60 min of extraction time and 2.91 g of sodium chloride. The desorption of the analytes was carried out using 30 μL of a mixture of toluene and hexane in the proportion of 60:40% (v/v) for 10 min. Detection limits in the range of 2.7–20.0 ng L−1, 0.50–1.15 μg kg−1, and 1.53–12.77 μg kg−1 were obtained for river water, strawberry and tomato samples, respectively. Good repeatability was obtained for all three sample types. The results suggest that the proposed procedure represents a very simple and low-cost microextraction alternative rendering adequate limits of quantification for the determination of organochlorine pesticides in environmental and food samples.  相似文献   

16.
A novel method of determining organochlorine pesticides (OCPs) is described. It is based on solid-phase microextraction (SPME) and gas chromatography–electron capture detection. During the development of the method, soil samples were prepared, spiked with standard solution, and then aged for some time. Extraction conditions such as the extraction time, the NaCl content, the volume of water, the extraction temperature and the desorption time were investigated and optimized. The limits of detection obtained using the method ranged from 0.10 to 0.51 ng g−1, and relative standard deviations were lower than 10% for most organochlorine pesticides. Real soil samples were successfully analyzed using the proposed method. The results from the method developed here were in good agreement with those obtained using ultrasonic extraction. The result demonstrates that aging soils spiked with standard solution is an important method development step, because the soil samples obtained using this approach are more like real soils than those obtained when aging is not used.   相似文献   

17.
Gao Z  Li W  Liu B  Liang F  He H  Yang S  Sun C 《Journal of chromatography. A》2011,1218(37):6285-6291
A novel nano-structured polyaniline-ionic liquid (i.e. 1-butyl-3-methylimidazolium hexafluorophosphate, BMIPF(6)) composite (BPAN) film coated steel wire was prepared by electrochemical deposition. Scanning electron microscopy images showed that the obtained porous BPAN coating consisted of nanofibers, whose diameter ranged from 50 to 80 nm. Furthermore, the novel nano-structured composite coating was very stable at relatively high temperatures (up to 350 °C) and it could be used for more 250 times without obvious decrease of the extraction efficiency. The novel BPAN coating was used for the headspace solid-phase microextraction (HS-SPME) of organochlorine pesticides (i.e. hexachlorocyolohexane, dichlorodiphenyldichloroethylene, dichlorodiphenyldichloroethane, dichlorodiphenyltrichloroethane), coupled with gas chromatography-electron capture detection (GC-ECD). The BPAN coating showed better analytical capability on the whole compared with common polyaniline (PANI) and polydimethylsiloxane (PDMS) coatings. The key parameters influencing extraction efficiency were investigated and optimized, including desorption time, stirring speed, extraction temperature, extraction time and ionic strength. The relative standard deviations (RSDs) for single fiber repeatability ranged from 2.3 to 8.7% (n=6) and the RSDs for fiber-to-fiber reproducibility (n=6) were 4.2-12.1%, respectively. The linear ranges exceeded three magnitudes with correlation coefficients above 0.99. The detection limits were 0.12-0.31 ng L(-1). The proposed method was successfully applied for the determination of organochlorine pesticides in lake water, waste water and sewage treatment plant effluent with good recoveries from 88.9 to 112.9%.  相似文献   

18.
An in-syringe ultrasound-assisted emulsification microextraction (USAEME) was developed for the extraction of organophosphorus pesticides (OPPs) from water samples. The OPPs subsequently analyzed gas chromatography (GC) using a microelectron capture detector (μECD). Ultrasound radiation was applied to accelerate the emulsification of μL-level low-density organic solvent in aqueous solutions to enhance the microextraction efficiency of OPPs in the sample preparation for GC-μECD. Parameters affecting the efficiency of USAEME, such as the extraction solvent, solvent volume, pH, salt-addition, and extraction time were thoroughly investigated. Based on experimental results, OPPs were extracted from a 5 mL aqueous sample by the addition of 20 μL toluene as the extraction solvent, followed by ultrasonication for 30 s, and then centrifugation for 3 min at 3200 rpm, offered the best extraction efficiency. Detections were linear in the concentration of 0.01–1 μg/L with detection limits between 1 ng/L and 2 ng/L for OPPs. Enrichment factors ranged from 330 to 699. Three spiked aqueous samples were analyzed, and recovery ranged from 90.1% to 104.7% for farm-field water, and 90.1% to 101.8% for industrial wastewater. The proposed method provides a simple, rapid, sensitive, inexpensive, and eco-friendly process for determining OPPs in water samples.  相似文献   

19.
The use of solid‐phase microextraction coatings based on gold nanoparticles was investigated, focusing the attention on the preparation of nanoparticles with nonclassical reduction agents of HAuCl4 such as gallic acid and H2O2, rather than the conventional sodium citrate. All nanoparticles were characterized by diode array spectroscopy, whereas novel nanoparticles prepared with gallic acid and H2O2 were also characterized by microscopic techniques. Solid‐phase microextraction coatings were prepared with a layer‐by‐layer approach. Gallic acid permitted the preparation of stable nanoparticles with milder experimental conditions (1 min, room temperature) and provided the most uniform coatings (thickness ∼3 μm). Seven organochlorine pesticides were determined in different environmental waters using gas chromatography with electron capture detection. Despite the low thickness of the coatings, limits of detection of the entire method down to 0.13 μg/L were obtained. A comparison with the commercial polyacrylate in terms of the partition coefficients of the analytes to the coatings gave logarithm of the partition coefficient values two times higher with gallic acid than polyacrylate (although the commercial fiber is 28 times thicker). Interfiber relative standard deviation values ranged from 8.67 to 21.3%. Optimum fibers also presented an adequate lifetime (>100 extractions).  相似文献   

20.
建立了一种USE-SPME-GC联用测定蔬菜中有机氯和菊酯类农药残留量的新方法,并对分析条件进行优化和探讨,实验表明,萃取液中基体杂质和色素对分析结果干扰较大,我们提出稀释的方法较好的解决这个问题。对实际蔬菜样品进行了测定和分析。  相似文献   

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