A novel solid-phase microextraction using coated fiber based sol-gel technique using poly(ethylene glycol) grafted multi-walled carbon nanotubes for determination of benzene, toluene, ethylbenzene and o-xylene in water samples with gas chromatography-flame ionization detector

In this study, poly(ethylene glycol) (PEG) grafted onto multi-walled carbon nanotubes (PEG-g-MWCNTs) were synthesized by the covalent functionalization of MWCNTs with hydroxyl-terminated PEG chains. For the first time, functionalized product of PEG-g-MWCNTs was used as selective stationary phase to prepare the sol-gel solid-phase microextraction (SPME) fiber in combination with gas chromatography-flame ionization detector (GC-FID) for the determination of ultra-trace levels of benzene, toluene, ethylbenzene and o-xylene (BTEX) in real water samples. The PEG-g-MWCNTs were characterized by Fourier transform infrared spectra and also thermo-gravimetric analysis, which verified that PEG chains were grafted onto the surface of the MWCNTs. The scanning electron micrographs of the fiber surface revealed a highly porous structure which greatly increases the surface area for PEG-g-MWCNTs sol-gel coating. This fiber demonstrated many inherent advantages, the main being the strong anchoring of the coating to the fused silica resulting from chemical bonding with the silanol groups on the fused-silica fiber surface. The new PEG-g-MWCNTs sol-gel fiber is simple to prepare, robust, with high thermal stability and long lifetime, up to 200 extractions. Important parameters influencing the extraction efficiency such as desorption temperature and time, extraction temperature, extraction time, stirring speed and salt effect were investigated and optimized. Under the optimal conditions, the method detection limits (S/N=3) were in the range of 0.6-3 pg mL(-1) and the limits of quantification (S/N=10) between 2 and 10 pg mL(-1). The relative standard deviations (RSDs) for one fiber (repeatability) (n=5) were obtained from 4.40 up to 5.75% and between fibers or batch to batch (n=3) (reproducibility) in the range of 4.31-6.55%. The developed method was successfully applied to real water samples while the relative recovery percentages obtained for the spiked water samples at 20 pg mL(-1) were from 90.21 to 101.90%.     

Multivariate optimization of surfactant‐assisted directly suspended droplet microextraction combined with GC for the preconcentration and determination of tramadol in biological samples

In this work, a novel procedure based on surfactant‐assisted directly suspended droplet microextraction for the determination of tramadol prior to GC with flame ionization detection is proposed. In this technique, a free microdroplet of solvent is transferred to the surface of an immiscible aqueous sample containing Triton X‐100 and tramadol while being agitated by a stirring bar placed on the bottom of the sample vial. After the predetermined time, the microdroplet of solvent is withdrawn by a syringe and analyzed. The effective parameters such as the type of organic solvent, extraction time, microdroplet volume, salt content of the donor phase, stirring speed, the source phase pH, concentration of Triton X‐100, and extraction temperature were optimized. For this purpose, a multivariate strategy was applied based on an experimental design in order to screen and optimize the significant factors. This method requires minimal sample preparation, analysis time, solvent consumption, and represents significant advantages over customary analytical methods. The linearity ranged from 10 to 2000 μg/L with RSDs (n = 5) of 7.3–10. Preconcentration factors and the LODs were 391–466 and 2.5–6.5 μg/L, respectively. Finally, this method was applied to the analysis of biological samples and satisfactory results were obtained.     

Determination of 3-nitroaniline in water samples by directly suspended droplet three-phase liquid-phase microextraction using 18-crown-6 ether and high-performance liquid chromatography

Liquid–liquid–liquid microextraction (LLLME) with directly suspended droplet in high-performance liquid chromatography (HPLC) has been applied as a new, rapid and easy method for the determination of 3-nitroaniline in environmental water samples. The target compound was extracted from the aqueous sample solution (donor phase, pH 13) into an organic phase and then was back-extracted into a directly suspended droplet of an acidic aqueous solution (acceptor phase, pH 0.3). In this method, without using a microsyringe as supporting device, an aqueous large droplet is freely suspended at the top-center position of an immiscible organic solvent, which is laid over the aqueous sample solution while being agitated. Then, the droplet was withdrawn into the microsyringe and directly was injected into the HPLC system with UV detection at 227 nm. Up to 148-fold enrichment of the analyte could be obtained under the optimal conditions [i.e. donor phase: 0.1 M sodium hydroxide solution (4.5 mL); organic phase: o-xylene/1-octanol (90:10, v/v; 250 μL); acceptor phase: 0.5 M hydrochloric acid and 500 mM 18-crown-6 ether (6 μL); extraction time: 60 s; back-extraction time: 6 min and stirring rate: 600 rpm]. The limit of detection was 1 μg/L (n = 7) and the relative standard deviation (RSD, n = 5) was 4.9 at S/N = 3. The calibration graph was linear in the range of 5–1500 μg/L with r = 0.9983. All experiments were carried out at room temperature (22 ± 0.5 °C).     

Directly suspended droplet microextraction in combination with microvolume UV-vis spectrophotometry for determination of phosphate

A miniaturized methodology for the determination of phosphate in waters has been developed by combining directly suspended droplet microextraction (DSDME) with microvolume spectrophotometry. The method is based on the extraction of the ion pair formed between 12-molybdophosphate and malachite green onto a microdrop of methyl isobutyl ketone and subsequent spectrophotometric determination with no dilution. An enrichment factor of 325 was obtained after 7.5 min of microextraction. The detection limit was 6.1 nM phosphate and the repeatability, expressed as relative standard deviation, was 2.7% (n = 6). The method was successfully applied to the determination of dissolved reactive phosphorus in different freshwater samples.     

Quantification of benzene,toluene, ethylbenzene and o-xylene in internal combustion engine exhaust with time-weighted average solid phase microextraction and gas chromatography mass spectrometry

A new and simple method for benzene, toluene, ethylbenzene and o-xylene (BTEX) quantification in vehicle exhaust was developed based on diffusion-controlled extraction onto a retracted solid-phase microextraction (SPME) fiber coating. The rationale was to develop a method based on existing and proven SPME technology that is feasible for field adaptation in developing countries. Passive sampling with SPME fiber retracted into the needle extracted nearly two orders of magnitude less mass (n) compared with exposed fiber (outside of needle) and sampling was in a time weighted-averaging (TWA) mode. Both the sampling time (t) and fiber retraction depth (Z) were adjusted to quantify a wider range of C_gas. Extraction and quantification is conducted in a non-equilibrium mode. Effects of C_gas, t, Z and T were tested. In addition, contribution of n extracted by metallic surfaces of needle assembly without SPME coating was studied. Effects of sample storage time on n loss was studied. Retracted TWA–SPME extractions followed the theoretical model. Extracted n of BTEX was proportional to C_gas, t, D_g, T and inversely proportional to Z. Method detection limits were 1.8, 2.7, 2.1 and 5.2 mg m⁻³ (0.51, 0.83, 0.66 and 1.62 ppm) for BTEX, respectively. The contribution of extraction onto metallic surfaces was reproducible and influenced by C_gas and t and less so by T and by the Z. The new method was applied to measure BTEX in the exhaust gas of a Ford Crown Victoria 1995 and compared with a whole gas and direct injection method.     

Determination of chlorophenols in environmental water samples using directly suspended droplet liquid-liquid-liquid phase microextraction prior to high-performance liquid chromatography

A new sample preparation method named directly suspended droplet liquid-liquid-liquid phase microextraction was used in this research for determination of three chlorophenols in environmental water samples. The analytes (2-chlorophenol, 3-chlorophenol and 4-chlorophenol) were extracted from 4.5?mL acidic donor phase, (pH 2, P1) into an organic phase, 350?µL?of benzene/1-octanol (90?:?10 v/v, P2) and then were back-extracted into a 7?µL droplet of an basic (pH 13) aqueous solution (acceptor phase, P3). In this method, contrary to the ordinary single drop liquid-phase microextraction technique, an aqueous large droplet is freely suspended on the surface of the organic solvent, without using a microsyringe as supporting device. This aqueous microdroplet is delivered at the top-centre position of an immiscible organic solvent which is laid over the aqueous donor sample solution while the solution is being agitated. Then, the acceptor phase containing chlorophenols was withdrawn back into a HPLC microsyringe and neutralised by adding of 7?µL HCl 0.1?M. The total amount was eventually injected into the HPLC system with UV detection at 225?nm for further analysis. Parameters such as the organic solvent, phases volumes, extraction and back-extraction times, stirring rate and pH values were optimised. The calibration graphs are linear in the range of 10–2000?µg?L^?1 with r?≥?0.9973. The enrichment factors were ranged from 115 to 170, and the limit of detection (LOD, n?=?7) varied from 5 to 10?µg?L^?1. The relative standard deviations (RSDs, n?=?5) were found 6.8 to 7.4 at S/N?=?3. All experiments were carried out at room temperature, (22?±?0.5°C).     

Determination of fuel dialkyl ethers and BTEX in water using headspace solid-phase microextraction and gas chromatography-flame ionization detection

A simple procedure for the determination of methyl tert-butyl ether (MTBE), ethyl tert-butyl ether (ETBE), ethyl butyl ether (EBE), tert-amyl methyl ether (TAME), benzene, toluene, ethylbenzene, and xylenes (BTEX) in water using headspace (HS) solid-phase microextraction (HS-SPME) was developed. The analysis was carried out by gas chromatography (GC) equipped with flame ionization detector (FID) and 100% dimethylpolysiloxane fused capillary column. A 2 Plackett-Burman design for screening and a central composite design (CCD) for optimizing the significant variables were applied. Fiber type, extraction temperature, sodium chloride concentration, and headspace volume were the significant variables. A 65 microm poly(dimethylsiloxane)-divinylbenzene (PDMS-DVB) SPME fiber, 10 degrees C, 300 g/l, and 20 ml of headspace (in 40 ml vial) were respectively chosen for the best extraction response. An extraction time of 10 min was enough to extract the ethers and BTEX. The relative standard deviation (R.S.D.) for the procedure varied from 2.6 (benzene) to 8.5% (ethylbenzene). The method detection limits (MDLs) found were from 0.02 (toluene, ethylbenzene, and xylenes) to 1.1 microg/l (MTBE). The optimized method was applied to the analysis of the rivers, marinas and fishing harbors surface waters from Gipuzkoa (North Spain). Three sampling were done in 1 year from June 2002 to June 2003. Toluene was the most detected analyte (in 90% of the samples analyzed), with an average concentration of 0.56 microg/l. MTBE was the only dialkyl ether detected (in 15% of the samples) showing two high levels over 400 microg/l that were related to accidental fuel spill.     

Directly suspended droplet microextraction with in injection-port derivatization coupled to gas chromatography-mass spectrometry for the analysis of polyphenols in herbal infusions, fruits and functional foods

A miniaturized liquid-phase extraction procedure based on directly suspended droplet microextraction is proposed for determining different classes of polyphenols. A derivatization reaction by means of in injection-port reaction with bis(trimethylsilyl)trifluoroacetamide is carried out to convert the polar non-volatile polyphenols into volatile derivatives. The separation and detection is carried out by coupling gas chromatography with mass spectrometry in the selected ion monitoring mode. The procedure uses undecanone, a low density organic solvent, and several factors influencing the extraction, collection efficiency and derivatization reaction are optimized. Excellent linearity was obtained for the range studied (0.05-500ngmL(-1)). The limits of detection are between 0.011 and 0.13ngmL(-1), depending on the compound, and the limits of quantification between 0.037 and 0.43ngmL(-1). The sensitivity and detection limits for polyphenols using the DSDME sample pretreatment method were very low. Enrichment factors are between 413 and 578. The recoveries obtained for spiked samples are satisfactory for all the compounds. The coupled miniaturized method is applied to the sensitive determination of both cis- and trans-resveratrol isomers, piceatannol, catechin, epicatechin, quercetin and fisetin in herbal infusions, fruits, juices and functional foods.     

Field analysis of benzene, toluene, ethylbenzene and xylene in water by portable gas chromatography-microflame ionization detector combined with headspace solid-phase microextraction

In this work, portable gas chromatography-microflame ionization detection (portable GC-μFID) coupled to headspace solid-phase microextraction (HS-SPME) was developed for the field analysis of benzene, toluene, ethylbenzene and xylene (BTEX) in water samples. The HS-SPME parameters such as fiber coating, extraction times, stirring rate, the ratio of headspace volume to sample volume, and sodium chloride concentration were studied. A 65 μm poly(dimethylsiloxane)-divinylbenzene (PDMS-DVB) SPME fiber, 900 rpm, 3.0 ml of headspace (1.0 ml water sample in 4.0 ml vial), and 35% sodium chloride concentration (w/v) were respectively chosen for the best extraction response. An extraction time of 1.0 min was enough to extract BTEX in water samples. The relative standard deviation (R.S.D.) for the procedure varied from 5.4% to 8.3%. The method detection limits (MDLs) found were lower than 1.5 μg/l, which was enough sensitive to detect the BTEX in water samples. The optimized method was applied to the field analysis of BTEX in wastewater samples. These experiment results show that portable GC-μFID combined with HS-SPME is a rapid, simple and effective tool for field analysis of BTEX in water samples.     

Hollow fiber liquid-phase microextraction coupled with gas chromatography-flame ionization detection for the profiling of fatty acids in vegetable oils

The development of a two phase hollow fiber liquid-phase microextraction technique, followed by gas-chromatography-flame ionization detection (GC-FID) for the profiling of the fatty acids (FAs) (lauric, myristic, palmitic, stearic, palmitoleic, oleic, linoleic, linolenic and arachidic) in vegetable oils is described. Heptadecanoic acid methyl ester was used as the internal standard. The FAs were transesterified to their corresponding methyl esters prior to the extraction. Extraction parameters such as type of extracting solvent, temperature, extraction time, stirring speed and salt addition were studied and optimized. Recommended conditions were extraction solvent, n-tridecane; extraction time, 35 min; extraction temperature, ambient; without addition of salt. Enrichment factors varying from 37 to 115 were achieved. Calibration curves for the nine FAs were well correlated (r(2)>0.994) within the range of 10-5000 μg L(-1). The limit of detection (signal:noise, 3) was 4.73-13.21 ng L(-1). The method was successfully applied to the profiling of the FAs in palm oils (crude, olein, kernel, and carotino cooking oil) and other vegetable oils (soybean, olive, coconut, rice bran and pumpkin). The encouraging enrichments achieved offer an interesting option for the profiling of the minor and major FAs in palm and other vegetable oils.     

Evaluation of the solid-phase microextraction fiber coated with single walled carbon nanotubes for the determination of benzene,toluene, ethylbenzene,xylenes in aqueous samples

A solid-phase microextraction (SPME) fiber coated with single walled carbon nanotubes (SWCNTs) was prepared by electrophoretic deposition and treated at 500 °C in H₂ stream. In order to evaluate the characteristics of the obtained fiber, it was applied in the headspace solid-phase microextraction (HS-SPME) of benzene, toluene, ethylbenzene and xylenes (BTEX) from water sample and quantification by gas chromatography with flame ionization detection (GC-FID). The results indicated that the thermal treatment with H₂ enhanced the extraction of the SWCNTs fiber for BTEX significantly. Thermal stability and durability of the fiber were also investigated, showing excellent stability up to 350 °C and life time over 120 times. In the comparison with the commercial CAR–PDMS fiber, the SWCNTs fiber showed similar and higher extraction efficiencies for BTEX. Under the optimized conditions, the linearity, LODs (S/N = 3) and LOQs (S/N = 10) of the method based on the SWCNTs fiber were 0.5–50.0, 0.005–0.026 and 0.017–0.088 μg/L, respectively. Repeatability for one fiber (n = 3) was in the range of 1.5–5.6% and fiber-to-fiber reproducibility (n = 3) was in the range of 4.2–8.3%. The proposed method was successfully applied in the analysis of BTEX compounds in seawater, tap water and wastewater from a paint plant.     

Comparative study of direct immersion and headspace single drop microextraction techniques for BTEX determination in water samples using GC-FID

In the present work the determination of benzene, toluene, ethylbenzene and o-xylene (BTEX) in environmental sample solutions using gas chromatography with flame ionisation detection (GC-FID) combined with three different sampling techniques, such as; direct single drop microextraction (DI-SDME), headspace single drop microextraction (HS-SDME) and ultrasonic assisted HS-SDME, were compared. In all of these techniques, for the determination of BTEX, the experimental parameters such as organic solvent effect, extraction time, agitation speed and salting effect were optimised. At their optimised conditions of operation the detection limits, times of extraction and precision for the three techniques are established. A detailed comparison of the analytical performance characteristics of these techniques for final GC-FID determination of BTEX in water samples was given. The technique provided a linear range of 50–20000?ng?mL^–1 for DI-SDME and 10–20000?ng?mL^–1 for HS-SDME methods, good repeatability (RSDs <4.72–7.74% for DI-SDME and 1.80–7.05% for HS-SDME (n?=?5), good linearity (r?≥?0.9978) and limits of detection (LODs) in the range of 0.006–10?ng?mL^?1 for DI-SDME, 0.1–3?ng?mL^–1 for HS-SDME methods (S/N?=?3). Then the optimised techniques were also applied to real samples (river and waste waters) containing BTEX and similar precision (RSD?<?8.2,?n?=?3) was obtained.     

Carbon nanotube field-effect transistor detector associated to gas chromatography for speciation of benzene,toluene, ethylbenzene, (o-, m- and p-)xylene

An analytical methodology based on a field-effect transistor detector using carbon nanotubes (NTFET) coupled to a gas chromatograph has been developed for the speciation of the following aromatic compounds: benzene, toluene, ethylbenzene, m-xylene, p-xylene and o-xylene (BTEX). This methodology combines the proven separation capability of gas chromatography (GC) with the potential for detection of a NTFET. The developed analyzer shows a high and stable analytical response upon repeated analysis of BTEX during 4 weeks, with detection limit less than 4 μg/L. The GC–NTFET system also shows a great suitability for actual monitoring of indoor atmospheres and no significant difference was observed between the results obtained by the developed analyzer and a more classical analytical methodology, namely gas chromatography–flame ionization detection (GC–FID).     

Separation of BTEX compounds (benzene,toluene, ethylbenzene and xylenes) from aqueous solutions using adsorption process

A commercial synthetic zeolite (Na-ZSM-5) was modified with an organic surfactant, HDTMA-Br. Then both unmodified and modified zeolite (SMZ-100) were tested to adsorb Benzene, Toluene, Ethylbenzene and Xylene (BTEX) compounds from water solution. Adsorption tests were done in batch conditions at the ambient temperature (20?°C) and pressure. Adsorbents were characterized using X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), N₂ adsorption-desorption isotherms and field emission scanning electron microscopy (FE-SEM) and characterization results proved the existence of surfactant on the surface of the adsorbent. In all cases, the modified zeolite sample, because of increasing the hydrophobicity of its surface, exhibited higher adsorption capacity in comparison with unmodified zeolite. Also, for each adsorbent, the adsorption capacity follows the order: E?>?X?>?T?>?B. In equilibrium experiments, Langmuir isotherm model fitted the equilibrium data better than the Freundlich model. In kinetic experiments, the pseudo-second order model described the kinetic data better than the other models.     

Separation and determination of amitriptyline and nortriptyline by dispersive liquid-liquid microextraction combined with gas chromatography flame ionization detection

Dispersive liquid–liquid microextraction (DLLME) coupled with gas chromatography–flame ionization detection (GC–FID) was applied for the determination of two tricyclic antidepressant drugs (TCAs), amitriptyline and nortriptyline, from water samples. This method is a very simple and rapid method for the extraction and preconcentration of these drugs from environmental sample solutions. In this method, the appropriate mixture of extraction solvent (18 μL Carbon tetrachloride) and disperser solvent (1 mL methanol) are injected rapidly into the aqueous sample (5.0 mL) by syringe. Therefore, cloudy solution is formed. In fact, it is consisted of fine particles of extraction solvent which is dispersed entirely into aqueous phase. The mixture was centrifuged and the extraction solvent is sedimented on the bottom of the conical test tube. 2.0 μL of the sedimented phase is injected into the GC for separation and determination of TCAs. Some important parameters, such as kind of extraction and disperser solvent and volume of them, extraction time, pH and ionic strength of the aqueous feed solution were optimized. Under the optimal conditions, the enrichment factors and extraction recoveries were between 740.04–1000.25 and 54.76–74.02%, respectively. The linear range was (0.005–16 μg mL⁻¹) and limits of detection were between 0.005 and 0.01 μg mL⁻¹ for each of the analytes. The relative standard deviations (R.S.D.) for 4 μg mL⁻¹ of TCAs in water were in the range of 5.6–6.4 (n = 6). The performance of the proposed technique was evaluated for determination of TCAs in blood plasma.     

A new porous-layer activated-charcoal-coated fused silica fiber: Application for determination of BTEX compounds in water samples using headspace solid-phase microextraction and capillary gas chromatography

Summary Extra-fine powdered activated charcoal has been used as stationary phase (coating layer) in solid-phase microextraction (SPME). The efficiency and reliability of the prepared device have been investigated for the extraction of some volatile organic compounds such as benzene, toluene, ethylbenzene and xylene isomers (BTEX) from the headspace of water samples. Monitoring of the extracted compounds and further quantitative analysis of the real samples have been performed by capillary GC-FID. Effects of several factors such as temperature, addition of salt, and stirring speed on extraction efficiency and exposure time have been studied. Under optimum conditions, extraction recoveries for these compounds from 50 mL water were >95%. The calibration graphs were linear in the range 5 to 10⁴ pg mL⁻¹ and the detection limit for each BTEX compound was 1.5–2 pg mL⁻¹. The results obtained by use of this porous layer activated charcoal (PLAC)-coated fiber have also been compared with results reported in the literature by use of a polydimethylsiloxane (PDMS)-coated fiber. Presented at the 21^st ISC held in Stuttgart, Germany, 15^th–20^th September, 1996     

Optimization of a novel method for determination of benzene, toluene, ethylbenzene, and xylenes in hair and waste water samples by carbon nanotubes reinforced sol-gel based hollow fiber solid phase microextraction and gas chromatography using factorial experimental design

A novel design of solid phase microextraction fiber containing carbon nanotube reinforced sol-gel which was protected by polypropylene hollow fiber (HF-SPME) was developed for pre-concentration and determination of BTEX in environmental waste water and human hair samples. The method validation was included and satisfying results with high pre-concentration factors were obtained. In the present study orthogonal array experimental design (OAD) procedure with OA(16) (4(4)) matrix was applied to study the effect of four factors influencing the HF-SPME method efficiency: stirring speed, volume of adsorption organic solvent, extraction and desorption time of the sample solution, by which the effect of each factor was estimated using individual contributions as response functions in the screening process. Analysis of variance (ANOVA) was employed for estimating the main significant factors and their percentage contributions in extraction. Calibration curves were plotted using ten spiking levels of BTEX in the concentration ranges of 0.02-30,000ng/mL with correlation coefficients (r) 0.989-0.9991 for analytes. Under the optimized extraction conditions, the method showed good linearity (0.3-20,000ng/L), repeatability, low limits of detections (0.49-0.7ng/L) and excellent pre-concentration factors (185-1872). The best conditions which were estimated then applied for the analysis of BTEX compounds in the real samples.     

Disposable ionic liquid coating for headspace solid-phase microextraction of benzene, toluene, ethylbenzene, and xylenes in paints followed by gas chromatography-flame ionization detection

Solid-phase microextraction (SPME) with a disposable ionic liquid (IL) coating was developed for headspace extraction of benzene, toluene, ethylbenzene, and xylenes (BTEX) in paints. The SPME fiber was coated with IL prior to every extraction, then the analytes were extracted and desorbed on the injection port of gas chromatography, and finally the IL coating on the fiber was washed out with solvents. The coating and washing out of IL from the fiber can be finished in a few minutes. This disposable IL-coated fiber was applied to determine BTEX in water-soluble paints with results in good agreement with that obtained by using commercially available SPME fibers. For all the four studied paints samples, the benzene contents were under the detection limits, but relatively high contents of toluene, ethylbenzene and xylenes (56-271 microg g(-1)) were detected with spiked recoveries in the range of 70-114%. Compared to the widely used commercially available SPME fibers, this proposed disposable IL-coated fiber has much lower cost per determination, comparable reproducibility (RSD < 11%), and no carryover between each determination. Considering that IL possess good extractability for various organic compounds and metals ions, and that task-specific IL can be designed and synthesized for selective extraction of target analytes, this disposable IL coating SPME might has great potential in sample preparation.     

Optimization of a single-drop microextraction procedure for the determination of organophosphorus pesticides in water and fruit juice with gas chromatography-flame photometric detection

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.     

Determining multi‐pesticide residues in teas by dispersive solid‐phase extraction combined with speed‐regulated directly suspended droplet microextraction followed by gas chromatography–tandem mass spectrometry

In this study, an effective speed‐regulated directly suspended droplet microextraction method was developed to condense pesticide residues from teas through dispersive solid‐phase extraction prior to analysis by gas chromatography with tandem mass spectrometry. The extractant was intentionally dispersed into the sample solution in the form of globules through high‐speed agitation. This procedure increases the contact area between the binary phases and shortens the distribution equilibrium time. The fine globules reassembled by decelerating stirring speed, the extractant could be taken out for gas chromatography with tandem mass spectrometry. Recovery studies were performed under optimized extraction conditions by using matrix blanks fortified with pesticides at three concentrations (10, 50, and 100 µg/kg). Over 87% of the recoveries for the analytes in four tea matrices were acceptable given their recovery ranges of 70–120% and relative standard deviations of ≤20%. The limits of quantification of most pesticides were lower than 10 µg/kg and thus satisfied the requirements for maximum residue levels prescribed by the European Community. A total of 38 tea samples from local markets were analyzed by using the proposed method. Results showed that chlorpyrifos was the most frequently detected pesticide in teas. The method is a potential choice for the routine monitoring of pesticide residues in complex matrices.