首页 | 本学科首页   官方微博 | 高级检索  
相似文献
 共查询到20条相似文献,搜索用时 15 毫秒
1.
Solid-phase microextraction method (SPME) coupled to GC/ECD has been developed and validated for the determination of phthalic acid esters (dimethyl-, diethyl-, di-n-butyl-, butylbenzyl-, di-2-ethylhexyl- and di-n-octyl phthalate) in water samples. Two types of coatings (PDMS, PA), altogether four different kinds of fibers have been investigated. Both parameters affecting the partition of analytes between a fiber coating and aqueous phase (i.e. extraction time, extraction temperature, agitation) and conditions of the thermal desorption in a GC injector were optimized. The final SPME method employing the polyacrylate fiber, extraction time 20 min, heating and stirring of the sample enabled the determination of all six phthalates in water samples. The method showed linear response over four orders of magnitude and the limits of quantification of the method ranged between 0.001 and 0.050 μg l−1. The repeatability expressed as R.S.D. was in the range 4-10% for the spiking level 7 μg l−1 of each analyte. The applicability of the developed SPME method was demonstrated for real water samples.  相似文献   

2.
A novel analytical method is presented for the determination of chlorophenols in water. This method involves pre-concentration by solid-phase microextraction (SPME) and an external desorption using a micellar medium as desorbing agent. Final analysis of the selected chlorophenols compounds was carried out by high-performance liquid chromatography (HPLC) with diode array detection (DAD). Optimum conditions for desorption, using the non-ionic surfactant polyoxyethylene 10 lauryl ether (POLE), such as surfactant concentration and time were studied. A satisfactory reproducibility for the extraction of target compounds, between 6 and 15%, was obtained, and detection limits were in the range of 1.1-5.9ngmL(-1). The developed method is evaluated and compared with the conventional one using organic solvent as a desorbing agent. The method was successfully applied to the determination of chlorophenols in water samples from different origin. This study has demonstrated that solid-phase microextraction with micellar desorption (SPME-MD) can be used as an alternative to conventional SPME method for the extraction of chlorophenols in water samples.  相似文献   

3.
A solid-phase microextraction (SPME) method for the ultra-trace determination of brominated phenols in aqueous samples has been developed and is reported for the first time to the best of our knowledge. 3,5,3',5'-tetrabromobisphenol A (TBBPA), the most widely used brominated flame retardant, and other phenolic flame retardants in commercial use, such as 2,4-dibromophenol (2,4-DBP), 2,4,6-tribromophenol (TBP) and pentabromophenol (PBP) have been included as target analytes. The analytical procedure involves the in situ acetylation-SPME and gas chromatography-mass spectrometry (GC-MS) determination of the target analytes. A multi-factor categorical experimental design was created to study the main parameters affecting the extraction efficiency, allowing also the evaluation of interaction effects between factors. The factors studied were type of fiber, extraction mode, exposing the fiber directly into the sample (DSPME) or into the headspace over the sample (HSSPME), and extraction temperature. Carboxen-polydimethylsiloxane (CAR-PDMS) fiber appeared to be the most suitable of the five fibers tested for the extraction of most compounds, excluding PBP and TBBPA for which polydimethylsiloxane (PDMS) was the most efficient coating. The highest response was achieved for both fibers sampling in headspace mode at 100 degrees C. In order to test the linearity of the method, calibration studies were performed with both CAR-PDMS and PDMS coatings. For both fibers, the method was linear in a range of 2 orders of magnitude, giving relative standard deviation (RSD%) below 10% for most compounds and detection limits at the low pg/mL level. In addition, the feasibility of the method for simultaneous determination of chlorinated and brominated phenols was studied. Finally, the method was applied to several real samples including tap water and effluent and influent waste water samples from an urban treatment plant, in which several phenolic compounds, such as phenol, methylphenols and chlorophenols, could be detected and quantified.  相似文献   

4.
Headspace solid-phase microextraction (HS-SPME) is proposed for isolating and determining the headspace volatiles formed during oxidation of fish-oil-in-water emulsions. Three different fiber coatings were tested and compared for sensitivity and reproducibility. A carboxen/polydimethylsiloxane (CAR-PDMS) fiber coating was found to be the most suitable for the analysis of emulsion volatiles. The main factors affecting the microextraction process on CAR-PDMS were then evaluated by a factorial design: amount of sample, time and temperature of extraction and stirring. The incubation of 0.5 g of emulsion at 60 degrees C during 30 min leads to the most effective extraction of volatiles associated with lipid oxidation of fish oil emulsions. The HS-SPME method coupled with GC-MS allowed the qualitative and quantitative analysis of the volatiles derived from oxidation of real fish oil enriched foods such as milk and mayonnaise. The method here proposed is very fast and simple and yields high sensitivity, with good repeatability for all target compounds.  相似文献   

5.
Polychlorinated biphenyls (PCBs) in water were extracted with a rebuilt extraction unit using 47 mm C18 solid-phase extraction (SPE) disks. Three types of disks (SPEC, ENVI and Empore) were investigated for the extraction of seven PCBs from 11 reagent water spiked at two concentration levels (20 and 1000 ng/l). The Empore disks produced the best analyte recoveries (91-107% with R.S.D. of 1-8%) at the low concentration level and displayed no leaking tendency. Empore disks were therefore considered superior to ENVI and SPEC disks for the conditions outlined in this work. The obtained extracts were dried and purified in an additional clean-up step using custom-made columns containing Florisil and Na2SO4. For water containing large amounts of organic matter, a pre-filtration was included. Final analysis was carried out on a dual-column GC-electron-capture detection system with on-column injection. The optimised extraction method, including clean-up, was less time-consuming and used less hazardous organic solvents than conventional liquid-liquid extraction (LLE) methods. Recoveries were 92-102% with R.S.D. of 3-8%.  相似文献   

6.
A solid-phase microextraction method (SPME) for determining trace levels of synthetic musk fragrances in residual waters has been developed. Six polycyclic musks (cashmeran, phantolide, celestolide, traseolide, galaxolide and tonalide), and a macrocyclic musk (ambrettolide) have been analysed. A detailed study of the different parameters affecting the extraction process is presented. The main important factors affecting the microextraction process have been studied and optimised by means of a categorical factorial design. Two extraction modes (direct SPME and headspace SPME) were tried at different extraction temperatures using four different fiber coatings [polydimethylsiloxane (PDMS), Carboxen (CAR)-PDMS, PDMS-divinylbenzene (DVB) and Carbowax (CW)-DVB]. An extraction temperature of 100 degrees C sampling the headspace over the sample using CAR-PDMS or PDMS-DVB as fiber coatings were found to be the experimental conditions that lead to a more effective extraction. The method proposed is very simple and yields high sensitivity, with detection limits in the low pg/ml, good linearity and repeatability for all the target compounds. The total analysis time, including extraction and GC analysis, was only 45 min. The optimised method performed well when it was applied to waste water from an urban treatment plant.  相似文献   

7.
《Analytica chimica acta》2004,506(1):71-80
We describe an estimation of measurement uncertainty calculated by the “bottom-up” approach for the determination of the oestrogenic compound nonylphenol in treated water samples by solid-phase extraction (SPE) and solid-phase microextraction (SPME) procedures and GC/MS detection. The results were compared and the different contributions to the uncertainty were evaluated. A study of the linear range was established and validation was performed for both methods using statistical analysis of several indicative parameters. In terms of validation data, precision (R.S.D. values <20%) and trueness (relative error <11%) were obtained for both methods under day-to-day conditions. The results of the estimation of measurement uncertainty obtained for both methods for concentrations higher than 1 μg/l have demonstrated that the time-consuming SPE method has a lower relative uncertainty (32%) than the SPME method (42.8%). The chromatographic uncertainty value was the main factor in the SPME method whereas the recovery factor (used to calculate the concentration) was the main contribution to uncertainty in the SPE method.  相似文献   

8.
In this paper, a polypropylene frit with porous network structure and high area-to-thickness ratio (4.8 mm diameter, 1.6 mm thickness, 20 mm pore size) was utilized as a mould of monolith. Poly(methacrylic acid-ethlyene glycol dimethacrylate) (MAA-EGDMA) monolith was in situ synthesized in the micro-channel of frit by photopolymerization. A monolith frit-based solid-phase microextraction method (SPME) was developed for the determination of hexanal and heptanal in serum samples by combining with high-performance liquid chromatography. 2,4-Dinitrophenylhydrazine (DNPH) as the derivatizing reagent was absorbed on a monolith frit, then its derivatization reaction with aldehydes and the absorption of formed hydrazones on the monolith disk occurred simultaneously. The condition parameters for polymerization, derivatization and extraction were optimized systematically. Under the optimum conditions, rigid structure, low back-pressure and high column capacity were achieved for the monolith frit. The limits of detection for hexanal and heptanal were 1.86 and 1.38 nmol/L, respectively. The inter- and intra-day relative standard deviations were less than 7.7% (n = 6). This method was applied successfully to aldehydes analysis in human serum samples. The method possesses advantages such as simplicity, efficiency, low cost and good biocompatibility. It provides an alternative approach for quantification of aldehydes in complex biological samples.  相似文献   

9.
A headspace solid-phase microextraction gas chromatography coupled with tandem mass spectrometry (HSSPME-GC-MS-MS) methodology for determination of brominated flame retardants in sediment and soil samples is presented. To the best of our knowledge, this is the first time that SPME has been applied to analyze polybrominated biphenyls (PBBs) and polybrominated diphenyl ethers (PBDEs) in environmental solid samples. Analyses were performed using 0.5-g solid samples moisturized with 2 mL water, employing a polydimethylsiloxane (PDMS) fiber coating, exposed to the headspace at 100 °C for 60 min. Several types of environmental solid samples were included in this study and the extraction efficiency was related to the organic matter content of the sample. Calibration was performed using real samples, and the method showed good linearity over a wide concentration range, precision, and afforded quantitative recoveries. The obtained detection limits were in the sub-ng g−1 for all the target analytes in both samples. The proposed procedure was applied to several marine and river sediments and soils, some of which were found to contain PBDEs at concentrations in the ng g−1 level; BDE-47, BDE-100, and BDE-99 were the major congeners detected. The proposed method constitutes a rapid and low-cost alternative for the analysis of the target brominated flame retardants in environmental solid samples, since the clean-up steps, fractionation, and preconcentration of extracts inherent to the classical multi-step solvent extraction procedures are avoided.   相似文献   

10.
A simple, fast and efficient liquid-liquid extraction (LLE) technique using headspace solid-phase microextraction (HS-SPME), in conjunction with gas chromatography-electron capture detection (GC-ECD) has been developed for the determination of haloacetic acids (HAAs) in tap water. The analytical procedure involves LLE, evaporation of extraction solvent to dryness, derivatization of HAAs into their methyl esters with acidic methanol, HS-SPME using 100-μm polydimethylsiloxane (PDMS) fiber, and GC-ECD determination. The derivatization process was optimized in dry conditions to achieve maximum sensitivity using the following conditions: esterification for 10 min at 55°C in 50 μL methanol, 30 μL sulphuric acid and 0.1 g anhydrous sodium sulphate. The HS-SPME conditions were also optimized and good sensitivity was obtained at a sampling temperature of 25°C, an absorption time of 10 min and a desorption time of 2 min. The linear calibration curves were observed for the concentration ranging from 0.1 to 200 μg/L with the correlation coefficients (R 2) greater than 0.993 and the relative standard deviation (RSD) less than 12%. The method detection limits of all analytes ranging from 0.02 to 0.7 μg/L were obtained. The proposed method is compared directly to standard EPA method 552.2 in drinking water, and significant advantage in terms of selectivity was observed. Finally the optimized procedure was applied to the analysis of HAAs in Bizerte drinking water. The studied HAA were detected in all the water samples and the concentration of total HAA5 ranged from 17.8 to 70.3 μg/L.  相似文献   

11.
A method for the determination of organophosphorus pesticides (diazinon, fenitrothion, fenthion, quinalphos, triazophos, phosalon and pyrazophos) in fruit (pears) and fruit juice samples was developed and validated. The samples were diluted with water, extracted by solid-phase microextraction (SPME) and analysed by gas chromatography (GC) using a flame photometric detector in phosphorous mode. Limits of detection of the method for fruit and fruit juice matrices were below 2 micrograms/kg for all pesticides. Relative standard deviations for triplicate analyses of samples fortified at 25 micrograms/kg of each pesticide were not higher than 8.7%. Recovery tests were performed for concentrations between 25 and 250 micrograms/kg. Mean recoveries for each pesticide were all above 75.9% and below 102.6% for juice, and between 70 and 99% for fruit except for pyrazophos in the fruit sample (with mean recovery of 53%). Therefore, the proposed method is applicable in the analysis of pesticides in fruit matrices and the use of the method in routine analysis of pesticide residues is discussed.  相似文献   

12.
A solid-phase microextraction (SPME) method has been developed for the determination of pentachlorophenol (PCP) in paper and board samples. The analytical procedure involves direct extraction of PCP from paper and board samples and determination by gas chromatography with electron capture detection (GC-ECD). Two kinds of commercially available fibres; 100 microm polydimethylsiloxane (PDMS), apolar, and 85 microm polyacrylate (PA), quite polar, were evaluated to determine the extraction efficiency of pentachlorophenol. Parameters affecting the extraction process, such as temperature and time, were studied. Moreover, time of desorption and the effect of addition of salt were also investigated. The optimized procedure was applied to the analysis of pentachlorophenol (PCP) in five samples of virgin and recycled paper and board. The PCP content was determined by GC-ECD. To evaluate the effectiveness of the proposed method, it was compared with conventional extraction method with liquid-liquid extraction and derivatization. Detection limit of 0.015 microg/g for PCP in paper was achieved with a RSD of 14%.  相似文献   

13.
The electrophoretic behaviour of ionizable and neutral alkylxanthines commonly used in pharmaceutical preparations was studied. The performance of various separation modes including capillary zone electrophoresis (CZE), cyclodextrin electrokinetic chromatography, and micellar electrokinetic chromatography (MEKC) with either sodium dodecyl sulfate (SDS) or bile salts as surfactants, was assessed. CZE in an alkaline medium successfully separates ionizable xanthines and dyphylline. The addition of carboxymethyl-β-cyclodextrin to the background electrolyte allows only partial resolution of neutral xanthines. Based on MEKC results, bile salts exhibit more discrimination ability than SDS to separate similar xanthines. The best results are provided by taurodeoxycholic acid, which ensures baseline separation of xanthines.  相似文献   

14.
Tri-, tetra- and pentachlorophenol (TCP, TeCP and PCP) can be considered the precursors in the formation of corresponding chloroanisoles, known to be powerful odorants in corks and wine. Determining the presence of these chlorophenolic compounds in cork soaking solutions (ethanol/water mixtures, 12% (v/v) ethanol used for cork quality control testing), or in wine can be achieved by acetylation/gas chromatography electron-capture detection. In order to reach the required sensitivity, a previous preconcentration step is necessary. Solid-phase extraction (SPE) and headspace solid-phase microextraction (HS-SPME) have given good results for the preconcentration of TCP, TeCP and PCP in such matrices. The use of Oasis HLB cartridges gives acceptable recoveries for the three compounds when different volumes (50-250 mL) of cork macerate with concentrations ranging from 20 to 150 ng/L are processed. Preconcentration based on HS-SPME has also been optimised with a 100 microm polydimethylsiloxane fibre and in situ derivatization. The HS-SPME method allows chlorophenols in a cork soaking solution and in wine to be determined with a limit of detection of 1 ng/L for each compound (in cork macerate) and a repeatability of around 0.5%-5% (n=8) for a concentration level of 30 ng/L.  相似文献   

15.
The feasibility of direct-immersion (DI) solid-phase microextraction (SPME) and headspace (HS) SPME for the determination of high-ring polycyclic aromatic hydrocarbons (PAHs) (4- to 6-ring PAHs) in water and soil samples is studied. Three SPME fibers--100- and 30-microm polydimethylsiloxane (PDMS) and 85-microm polyacrylate (PA) fibers-are compared for the effective extraction of PAHs. Parameters affecting the sorption of PAHs into the fiber such as sampling time, sampling volume, and temperature are also evaluated. The extracted amounts of high-ring PAHs decrease with the decreasing of film thickness, and the 100-microm PDMS has the highest extraction efficiency than 85-microm PA and 30-microm PDMS fibers. Also, the extraction efficiency decreases with the increasing molecular weights of PAHs. Of the 10 high-ring PAHs, only fluoranthene and pyrene can reach equilibrium within 120 min at 25 degrees C for DI-SPME in a water sample. Increasing the temperature to 60 degrees C can increase the sensitivity of PAHs and shorten the equilibrium time. A 0.7- to 25-fold increase in peak area is obtained for DI-SPME when the working temperature is increased to 60 degrees C. For HS-SPME, the extraction efficiency of PAHs decrease when the headspace volume of the sampling system increases. All high-ring PAHs can be detected in a water sample by increasing the temperature to 80 degrees C. However, only 4- and 5-ring PAHs can be quantitated in a CRM soil sample when HS-SPME is used. The addition of a surfactant with high hydrophilic property can effectively enhance the sensitivity of high-ring PAHs. HS-SPME as well as DI-SPME with 100-microm PDMS or 85-microm PA fibers are shown to be suitable methods for analyzing high-ring PAHs in a water sample; however, this technique can only apply in a soil sample for PAHs having up to 5 rings.  相似文献   

16.
The feasibility of solid-phase microextraction (SPME) for the determination of several organophosphorus flame retardants and plastizicers in water samples by gas chromatography-nitrogen phosphorous detection (GC-NPD) is evaluated. These compounds have a wide range of polarities and volatilities and require a thorough optimisation of the different SPME parameters. Considering also possible contamination and carryover sources, the best compromise microextraction conditions were found to be direct extraction of 22 ml samples, containing 300 mg/ml of NaCl, with a PDMS-DVB coated fibre at room temperature. Although equilibrium was not achieved, an extraction time of 40 min allowed obtaining a good sensitivity (quantification limits between 0.010 and 0.025 ng/ml), comparable to that achieved by solid-phase extraction (SPE) of 1l samples, producing both similar values of precision and accuracy. Furthermore, the SPME method has shown to be free of matrix effects, avoiding the need of employing the standard addition procedure for quantification, and was suitable for the determination of eight of the nine considered compounds. Only tris-(2-ethylhexyl)-phosphate was neither determinable by SPME nor by SPE. Finally, the application of the developed methodology to the analysis of wastewater samples, showed that important concentrations of these compounds (up to 10 ng/ml) have been detected in treated sewage water, being discharged into the aquatic environment.  相似文献   

17.
Water contamination due to the wide variety of pesticides used in agriculture practices is a global environmental pollution problem. The 98/83 European Directive requires the measurement of pesticides residues at a target concentration of 1.0 microg/l in surface water and 0.1 microg/l in drinking water. In order to reach the level of detection required, efficient extraction techniques are necessary. The application of a new extraction technique: single-drop microextraction (SDME), followed by gas chromatography with electron-capture detection, was assessed for determining alpha-endosulfan and beta-endosulfan in water samples. Experimental parameters which control the performance of SDME, such as selection of microextraction solvent and internal standard, optimization of organic drop volume, effects of sample stirring, temperature and salt addition, and sorption time profiles were studied. Once SDME was optimized, analytical parameters such as linearity, precision, detection and quantitation limits, plus matrix effects were evaluated. The SDME method was compared with solid-phase microextraction and solid-phase extraction with the aim of selecting the most appropriate method for a certain application.  相似文献   

18.
A fast, inexpensive and efficient sample preparation method for the determination of 10 organophosphorus compounds in water samples is presented. Analytes were extracted using the dispersive liquid-liquid microextraction (DLLME) technique and determined by gas chromatography with nitrogen-phosphorus detection (GC-NPD). The influence of several variables (e.g. type and volume of dispersant and extraction solvents, ionic strength, shaking time and mode, etc.) on the performance of the sample preparation step was carefully evaluated. Under final working conditions, 1 mL of acetone containing a 2% of 1,1,1-trichloroethane (20 microL) was added to 10 mL of water with 20% of sodium chloride. The ternary mixture was centrifuged at 3500 rpm to allow phase separation. After removing the aqueous supernatant, an aliquot of the settled extract was injected in the GC-NPD system. Under the above conditions, the method provided enrichment factors between 190 and 830 times (depending on the considered compound), relative standard deviations below 10%, except for tris(2-ethylhexyl) phosphate (TEHP), and quantification limits between 0.01 and 0.08 ng/mL. Matrix effects were assessed using different water samples, and accuracy was evaluated by comparison with solid-phase microextraction.  相似文献   

19.
Synthetic musks are extensively used as fragrance components in a wide range of consumer and personal care products such as detergents, shampoos, perfumes and other cosmetic products. Amongst them, galaxolide and tonalide have become ubiquitous pollutants due to their continuous releasing into the environment. Because of their nature as artificial fragrances, inhalation should be considered as an important exposure pathway, especially in indoor environments. However, up to now very few studies have been carried out to determine these emergent pollutants indoors. In this work, a simple and highly sensitive methodology for the analysis of synthetic musk fragrances in indoor air samples is presented. The proposed methodology combines solid-phase extraction (SPE) and solid-phase microextraction (SPME), followed by gas chromatography-mass spectrometry (GC/MS). To the best of our knowledge, this is the first method based on SPME for the analysis of musks in air. By active sampling, musks present in air were adsorbed onto 25mg Tenax and then transferred to a SPME fiber in the headspace mode (HS). An experimental design strategy was used to optimize main factors potentially affecting the microextraction process such as fiber coating, temperature and the addition of a microvolume of organic solvent to the solid sorbent prior to SPME. Breakthrough of the SPE sorbent was studied from 1 to 10m(3) without significant losses. Recovery studies were performed at two concentration levels (2 and 20ngm(-3)), obtaining quantitative recoveries (>/=85%) by external calibration. A comprehensive study was performed in order to estimate the limits of detection taking into account the contamination risks and laboratory blanks. Values at the sub ngm(-3) level were achieved for all the target compounds sampling 5m(3) air. External calibration, not requiring the complete sampling process, demonstrated to be suitable for the quantification of all musk compounds. Finally, several indoor environments were analyzed using the proposed method.  相似文献   

20.
Aldehydes are produced in water disinfected primarily by ozone treatment, and are generally present in treated water below the limit of detection (<5 μg L−1) of commonly proposed methods. Formaldehyde is the most studied along with acetaldehyde due to their mutagenic character, and because it causes chromosomal aberrations. This paper reports the first miniaturised system for the simultaneous determination of thirteen aldehydes (aliphatic and aromatic) which are selected based on their frequent or suspected presence in water, mainly as disinfection by-products (DBPs). The micro liquid–liquid extraction (MLLE) method is a miniaturisation of EPA Method 556.1 for carbonyl compounds that includes some innovations, such as performing the derivatising reaction in a strong acidic medium (pH 1.1), and the addition of magnesium sulphate to the aqueous layer as the heating agent, which allows to carry out the whole simultaneous derivatisation/microextraction process in only 1 min. Large-volume sample injection (50 μL) coupled to programmed temperature vaporiser–gas chromatography–mass spectrometry is also used to improve both sensitivity and selectivity. The MLLE method demonstrated high extraction efficiency (96%) with low limits of detection, between 0.7 and 80 ng L−1, and good precision (RSD below 10%, n = 11). The proposed method was evaluated by determining aldehydes in water. Our study demonstrated that the selection of the target aldehydes was appropriate since all were found (at average concentrations from 8.0 to 1.4 μg L−1 for aliphatic and aromatic aldehydes, respectively) in swimming pool waters as DBPs.  相似文献   

设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号