Hollow fiber supported ionic liquid membrane microextraction for determination of sulfonamides in environmental water samples by high-performance liquid chromatography

By using ionic liquid as membrane liquid and tri-n-octylphosphine oxide (TOPO) as additive, hollow fiber supported liquid phase microextraction (HF-LPME) was developed for the determination of five sulfonamides in environmental water samples by high-performance liquid chromatography with ultraviolet detection The extraction solvent and the parameters affecting the extraction enrichment factor such as the type and amount of carrier, pH and volume ratio of donor phase and acceptor phase, extraction time, salt-out effect and matrix effect were optimized. Under the optimal extraction conditions (organic liquid membrane phase: [C₈MIM][PF₆] with 14% TOPO (w/v); donor phase: 4 mL, pH 4.5 KH₂PO₄ with 2 M Na₂SO₄; acceptor phase: 25 μL, pH 13 NaOH; extraction time: 8 h), low detection limits (0.1–0.4 μg/L, RSD ≤ 5%) and good linear range (1–2000 ng/mL, R² ≥ 0.999) were obtained for all the analytes. The presence of humic acid (0–25 mg/L dissolved organic carbon) and bovine serum albumin (0–100 μg/mL) had no significant effect on the extraction efficiency. Good spike recoveries over the range of 82.2–103.2% were obtained when applying the proposed method on five real environmental water samples. These results indicated that this present method was very sensitive and reliable with good repeatabilities and excellent clean-up in water samples. The proposed method confirmed hollow fiber supported ionic liquid membrane based LPME to be robust to monitoring trace levels of sulfadiazine, sulfamerazine, sulfamethazine, sulfadimethoxine and sulfamethoxazole in aqueous samples.     

Carbon nanotube reinforced hollow fiber solid/liquid phase microextraction: A novel extraction technique for the measurement of caffeic acid in Echinacea purpurea herbal extracts combined with high-performance liquid chromatography

A new design of hollow fiber solid–liquid phase microextraction (HF-SLPME) was developed for the determination of caffeic acid in medicinal plants samples as Echinacea purpure. The membrane extraction with sorbent interface used in this research is a three-phase supported liquid membrane consisting of an aqueous (donor phase), organic solvent/nano sorbent (membrane) and aqueous (acceptor phase) system operated in direct immersion sampling mode. The multi-walled carbon nanotube dispersed in the organic solvent is held in the pores of a porous membrane supported by capillary forces and sonification. It is in contact with two aqueous phases: the donor phase, which is the aqueous sample, and the acceptor phase, usually an aqueous buffer. All microextraction experiments were supported using an Accurel Q3/2 polypropylene hollow fiber membrane (600 μm I.D., 200 μm wall thicknesses, and 0.2 μm pore size). The experimental setup is very simple and highly affordable. The hollow fiber is disposable, so single use of the fiber reduces the risk of cross-contamination and carry-over problems. The proposed method allows the very effective and enriched recuperation of an acidic analyte into one single extract. In order to obtain high enrichment and extraction efficiency of the analyte using this novel technique, the main parameters were optimized. Under the optimized extraction conditions, the method showed good linearity (0.0001–50 μg/L), repeatability, low limits of detection (0.00005 μg/L) and excellent enrichment (EF = 2108).     

Application of dynamic liquid-phase microextraction and injection port derivatization combined with gas chromatography–mass spectrometry to the determination of acidic pharmaceutically active compounds in water samples

A method has been established for the determination of four pharmaceutically active compounds (ibuprofen, ketoprofen, naproxen and clofibric acid) in water samples using dynamic hollow fiber liquid-phase microextraction (HF/LPME) followed by gas chromatography (GC) injection port derivatization and GC–mass spectrometric (MS) determination. Dynamic HF/LPME is a novel approach to microextraction that involves the use of a programmable syringe pump to move the liquid phases participating in the extraction so as to facilitate the process. Trimethylanilinium hydroxide (TMAH) was used as derivatization reagent for the analytes to increase their volatility and improve chromatographic separation. Parameters that affect extraction efficiency (selection of organic solvent, volume of organic solvent, agitation in the donor phase, plunger movement and extraction time) were investigated. Under optimal conditions, the proposed method provided good enrichment factors up to 251, reproducibility ranging from 3.26% to 10.61%, and good linearity from 0.2 to 50 μg/L. The limits of detection ranged between 0.01 and 0.05 μg/L (S/N = 3) using selective ion monitoring. This method was applied to the determination of the four pharmaceutically active compounds in tap water and wastewater collected from a drain in the vicinity of a hospital.     

Automated polyvinylidene difluoride hollow fiber liquid-phase microextraction of flunitrazepam in plasma and urine samples for gas chromatography/tandem mass spectrometry

A new polyvinylidene difluoride (PVDF) hollow fiber (200 μm wall thickness, 1.2 mm internal diameter, 0.2 μm pore size) was compared with two other polypropylene (PP) hollow fibers (200, 300 μm wall thickness, 1.2 mm internal diameter, 0.2 μm pore size) in the automated hollow fiber liquid-phase microextraction (HF-LPME) of flunitrazepam (FLNZ) in biological samples. With higher porosity and better solvent compatibility, the PVDF hollow fiber showed advantages with faster extraction efficiency and operational accuracy. Parameters of the CTC autosampler program for HF-LPME in plasma and urine samples were carefully investigated to ensure accuracy and reproducibility. Several parameters influencing the efficiency of HF-LPME of FLNZ in plasma and urine samples were optimized, including type of porous hollow fiber, organic solvent, agitation rate, extraction time, salt concentration, organic modifier, and pH. Under optimal conditions, extraction recoveries of FLNZ in plasma and urine samples were 6.5% and 83.5%, respectively, corresponding to the enrichment factor of 13 in plasma matrix and 167 in urine matrix. Excellent sample clean-up was observed and good linearities (r² = 0.9979 for plasma sample and 0.9995 for urine sample) were obtained in the range of 0.1–1000 ng/mL (plasma sample) and 0.01–1000 ng/mL (urine sample). The limits of detection (S/N = 3) were 0.025 ng/mL in plasma matrix and 0.001 ng/mL in urine matrix by gas chromatography/mass spectrometry/mass spectrometry.     

Determination of fungicides in water using liquid phase microextraction and gas chromatography with electron capture detection

A hollow fiber liquid phase microextraction (HF-LPME) and gas chromatographic-electron capture detection (GC-ECD) method for the determination of six fungicides (chlorothalonil, hexaconazole, penconazole, procymidone, tetraconazole, and vinclozolin) in 3 ml of water was described. The method used 3 μl of toluene as extraction solvent, 20 min extraction time with pH 4, stirring at 870 rpm, and no salt addition. The enrichment factors of this method were from 135 to 213. Limits of detection were in the range of 0.004-0.025 μg/l. The relative standard deviations (RSDs) at 0.1 and 5 μg/l of spiking levels were in the range 3-8%. Recoveries of six fungicides from farm water at a spiking level of 0.5 μg/l were between 90.7 and 97.6%. The method compared favorably with the traditional method in terms of the sample size, analysis time, and cost.     

Determination of endocrine-disrupting compounds in water by carbon nanotubes solid-phase microextraction fiber coupled online with high performance liquid chromatography

The commercial solid phase microextraction (SPME) fibers are not stable enough in organic solvent and tend to swell and strip off from the silica fiber in the high performance liquid chromatography (HPLC) mobile phase, and therefore the application of SPME coupled online with HPLC is limited. In this study, an SPME fiber coated with single walled carbon nanotubes (SWCNTs), prepared by means of electrophoretic deposition, was coupled on line to HPLC for the determination of four endocrine-disrupting compounds, i.e. bisphenol A (BPA), estrone (E₁), 17α-ethynylestradiol (EE₂) and octylphenol (OP), in aqueous samples. The results showed that the SWCNTs coating on the prepared fiber did not swell and strip off from the platinum fiber throughout the experiment, thus indicating a high resistance to the HPLC mobile phase, the mixture of water and acetonitrile. The SWCNTs fiber had similar (for OP) or higher (for BPA, EE₂ and E₁) extraction efficiencies than the commonly used polyacrylate fiber, and had a lifetime of more than 120 operation times. Under the optimized conditions, the linearity of the proposed method was 1.0-30.0 μg/L for BPA and OP and 3.0-90.0 μg/L for E₁ and EE₂. The limits of detection (LODs; S/N = 3) and limits of quantification (LOQs; S/N = 10) of the method were 0.32-0.52 μg/L and 1.06-1.72 μg/L, respectively. Repeatability for one fiber (n = 3) was in the range of 1.3-7.1% and fiber-to-fiber reproducibility (n = 3) was in the range of 1.6-8.4%. The proposed method was successfully applied for the analysis of spiked tap water and seawater samples with recoveries from 81.8 to 97.3%.     

Hollow fiber-based liquid phase microextraction combined with high-performance liquid chromatography for extraction and determination of some antidepressant drugs in biological fluids

The applicability of hollow fiber-based liquid phase microextraction (HF-LPME) was evaluated for the extraction and preconcentration of three antidepressant drugs (amitriptyline, imipramine and sertraline) prior to their determination by HPLC-UV. The target drugs were extracted from 11.0 mL of aqueous solution with pH 12.0 (source phase) into an organic extracting solvent (n-dodecane) impregnated in the pores of a hollow fiber and finally back extracted into 24 μL of aqueous solution located inside the lumen of the hollow fiber and adjusted to pH 2.1 using 0.1 M of H₃PO₄ (receiving phase). The extraction was performed due to pH gradient between the inside and outside of the hollow fiber membrane. In order to obtain high extraction efficiency, the parameters affecting the HF-LPME including pH of the source and receiving phases, the type of organic phase, ionic strength and volume of the source phase, stirring rate and extraction time were studied and optimized. Under the optimized conditions, enrichment factors up to 300 were achieved and the relative standard deviation (R.S.D.%) of the method was in the range of 2-12%. The calibration curves were obtained in the range of 5-500 μg L⁻¹ with reasonable linearity (R² > 0.998) and the limits of detection (LODs) ranged between 0.5 and 0.7 μg L⁻¹ (based on S/N = 3). Finally, the applicability of the proposed method was evaluated by extraction and determination of the drugs in urine, plasma and tap water samples. The results indicated that hollow fiber microextraction method has excellent clean-up and high-preconcentration factor and can be served as a simple and sensitive method for monitoring of antidepressant drugs in the biological samples.     

Commercial polymeric fiber as sorbent for solid-phase microextraction combined with high-performance liquid chromatography for the determination of polycyclic aromatic hydrocarbons in water

A novel microextraction method making use of commercial polymer fiber as sorbent, coupled with high-performance liquid chromatography-fluorescence detection for the determination of polycyclic aromatic hydrocarbons (PAHs) in water has been developed. In this technique, the extraction device was simply a length (8 cm) of a strand of commercial polymer fiber, Kevlar (each strand consisted of 1000 filaments, each of diameter ca. 9.23 μm), that was allowed to tumble freely in the aqueous sample solution during extraction. The extracted analytes were desorbed ultrasonically before the extract was injected into HPLC system for analysis. Extraction parameters such as extraction time, desorption time, type of desorption solvent and sample volume were optimized. Each fiber could be used for up to 50 extractions and the method showed good precision, reproducibility and linear response within a concentration range 0.05–5.00 μg L⁻¹ with correlation coefficients of up to 0.9998. Limits of detection between 0.4 and 4.4 ng L⁻¹ for seven PAHs could be achieved. The relative standard deviations (n = 3) of this technique were between 2.9% and 12.1%.     

In situ growth and phenyl functionalization of titania nanoparticles coating for solid-phase microextraction of ultraviolet filters in environmental water samples followed by high performance liquid chromatography–UV detection

Based on TiO₂-nanoparticles coating fabricated by a one-step anodization method on titanium wire substrate, a novel phenyl functionalized solid-phase microextraction (SPME) fiber coating was prepared by simple and rapid in situ chemical assembling technique between the fiber surface titanol groups and trichlorophenylsilane reaction. The as-fabricated fiber exhibited good extraction capability for some UV filters and was employed to determine the ultraviolet (UV) filters in combination with high performance liquid chromatography–UV detection (HPLC–UV). The main parameters affecting extraction performance were investigated and optimized. Under the optimized conditions, the developed method was applied to detect several UV filters at trace concentration levels with only 8 mL of sample volume. They were determined in the range from 0.005 to 25 μg L⁻¹ with detection limits (S/N = 3) from 0.1 to 50 ng L⁻¹. The relative standard deviations (RSDs) for single fiber repeatability varied from 4.6 to 6.5% (n = 5) and fiber-to-fiber reproducibility (n = 5) ranged from 5.5 to 9.1%. The linear ranges spanned two-four magnitudes with correlation coefficients above 0.9990. Five real water samples including four Yellow River water samples and one rain water sample were determined sensitively with good recoveries ranging from 86.2 to 105.5%. The functionalized fiber coating performed good reproducible manner, high mechanical strength, good stability and long service life. Moreover, this study proposed an efficient sample pretreatment method for the determination of UV filters from environmental water samples.     

High extraction efficiency for polar aromatic compounds in natural water samples using multiwalled carbon nanotubes/Nafion solid-phase microextraction coating

A novel solid-phase microextraction (SPME) fiber coated with multiwalled carbon nanotubes (MWCNTs)/Nafion was developed and applied for the extraction of polar aromatic compounds (PACs) in natural water samples. The characteristics and the application of this fiber were investigated. Electron microscope photographs indicated that the MWCNTs/Nafion coating with average thickness of 12.5 μm was homogeneous and porous. The MWCNTs/Nafion coated fiber exhibited higher extraction efficiency towards polar aromatic compounds compared to an 85 μm commercial PA fiber. SPME experimental conditions, such as fiber coating, extraction time, stirring rate, desorption temperature and desorption time, were optimized in order to improve the extraction efficiency. The calibration curves were linear from 0.01 to 10 μg mL⁻¹ for five PACs studied except p-nitroaniline (from 0.005 to 10 μg mL⁻¹) and m-cresol (from 0.001 to 10 μg mL⁻¹), and detection limits were within the range of 0.03–0.57 ng mL⁻¹. Single fiber and fiber-to-fiber reproducibility were less than 7.5 (n = 7) and 10.0% (n = 5), respectively. The recovery of the PACs spiked in natural water samples at 1 μg mL⁻¹ ranged from 83.3 to 106.0%.     

Dispersive liquid–liquid microextraction combined with high-performance liquid chromatography-UV detection as a very simple,rapid and sensitive method for the determination of bisphenol A in water samples

Dispersive liquid–liquid microextraction (DLLME) coupled with high-performance liquid chromatography (HPLC)-UV detection was applied for the extraction and determination of bisphenol A (BPA) in water samples. An appropriate mixture of acetone (disperser solvent) and chloroform (extraction solvent) was injected rapidly into a water sample containing BPA. After extraction, sedimented phase was analyzed by HPLC-UV. Under the optimum conditions (extractant solvent: 142 μL of chloroform, disperser solvent: 2.0 mL of acetone, and without salt addition), the calibration graph was linear in the range of 0.5–100 μg L⁻¹ with the detection limit of 0.07 μg L⁻¹ for BPA. The relative standard deviation (RSD, n = 5) for the extraction and determination of 100 μg L⁻¹ of BPA in the aqueous samples was 6.0%. The results showed that DLLME is a very simple, rapid, sensitive and efficient analytical method for the determination of trace amount of BPA in water samples and suitable results were obtained.     

Simultaneous conduction of two- and three-phase hollow-fiber-based liquid-phase microextraction for the determination of aromatic amines in environmental water samples

This paper describes a simultaneously performed two-/three-phase hollow-fiber-based liquid-phase microextraction (HF-LPME) method for the determination of aromatic amines with a wide range of pK_a (−4.25 to 4.6) and log K_OW (0.9–2.8) values in environmental water samples. Analytes including aniline, 4-nitroaniline, 2,4-dinitroaniline and dicloran were extracted from basic aqueous samples (donor phase, DP) into the microliter volume of organic membrane phase impregnated into the pores of the polypropylene hollow fiber wall, then back extracted into the acidified aqueous solution (acceptor phase, AP) filling in the lumen of the hollow fiber. The mass transfer of the analytes from the donor phase through the organic membrane phase into acceptor phase was driven by both the counter-coupled transport of hydrogen ions and the pH gradient. Afterwards, the hollow fiber was eluted with 50 μL methanol to capture the analytes from both the organic membrane and the acceptor phase. Factors relevant to the enrichment factors (EFs) were investigated. Under the optimized condition (DP: 100 mL of 0.1 M NaOH with 2 M Na₂SO₄; organic phase: di-n-hexyl with 8% trioctylphosphine oxide (TOPO); AP: 10 μL of 8 M HCl; extraction time of 80 min), the obtained EFs were 405–2000, dynamic linear ranges were 5–200 μg/L (R > 0.9976), and limits of detection were 0.5–1.5 μg/L. The presence of humic acid (0–25 mg/L dissolved organic carbon) had no significant effect on the extraction efficiency. The proposed procedure worked very well for real environmental water samples with microgram per liter level of analytes, and good spike recoveries (80–103%) were obtained.     

Cork as a new (green) coating for solid-phase microextraction: Determination of polycyclic aromatic hydrocarbons in water samples by gas chromatography–mass spectrometry

A new fiber for solid-phase microextraction (SPME) was prepared employing cork as a coating. The morphology and composition of the cork fiber was evaluated by scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR), respectively. The proposed fiber was used for the determination of polycyclic aromatic hydrocarbons (PAHs) in river water samples by gas chromatography–selected ion monitoring–mass spectrometry (GC–SIM–MS). A central composite design was used for optimization of the variables involved in the extraction of PAHs from water samples. The optimal extraction conditions were extraction time and temperature of 60 min and 80 °C, respectively. The detection and quantification limits were 0.03 and 0.1 μg L⁻¹, respectively. The recovery values were between 70.2 and 103.2% and the RSD was ≤15.7 (n = 3). The linear range was 0.1–10 μg L⁻¹ with r ≥ 0.96 and the fiber-to-fiber reproducibility showed RSD ≤ 18.6% (n = 5). The efficiency of the cork fiber was compared with commercially available fibers and good results were achieved, demonstrating the applicability and great potential of cork as a coating for SPME.     

Hollow fiber liquid-phase microextraction for the determination of trace amounts of rosiglitazone (anti-diabetic drug) in biological fluids using capillary electrophoresis and high performance liquid chromatographic methods

A three-phase hollow fiber liquid-phase microextraction (HF-LPME) coupled either with capillary electrophoresis (CE) or high performance liquid chromatography (HPLC) with UV detection methods was successfully developed for the determination of trace levels of the anti-diabetic drug, rosiglitazone (ROSI) in biological fluids. The analyte was extracted into dihexyl ether that was immobilized in the wall pores of a porous hollow fiber from 10 mL of aqueous sample, pH 9.5 (donor phase), and was back extracted into the acceptor phase that contained 0.1 M HCl located in the lumen of the hollow fiber. Parameters affecting the extraction process such as type of extraction solvent, HCl concentration, donor phase pH, extraction time, stirring speed, and salt addition were studied and optimized. Under the optimized conditions (extraction solvent, dihexyl ether; donor phase pH, 9.5; acceptor phase, 0.1 M HCl; stirring speed, 600 rpm; extraction time, 30 min; without addition of salt), enrichment factor of 280 was obtained. Good linearity and correlation coefficients of the analyte was obtained over the concentration ranges of 1.0–500 and 5.0–500 ng mL⁻¹ for the HPLC (r² = 0.9988) and CE (r² = 0.9967) methods, respectively. The limits of detection (LOD) and limits of quantitation (LOQ) for the HPLC and CE methods were (0.18, 2.83) and (0.56, 5.00) ng mL⁻¹, respectively. The percent relative standard deviation (n = 6) for the extraction and determination of three concentration levels (10, 250, 500 ng mL⁻¹) of ROSI using the HPLC and CE methods were less than 10.9% and 13.2%, respectively. The developed methods are simple, rapid, sensitive and are suitable for the determination of trace amounts of ROSI in biological fluids.     

Part-per-trillion determination of chlorobenzenes in water using dispersive liquid-liquid microextraction combined gas chromatography-electron capture detection

In this study, a simple, rapid and efficient method, dispersive liquid-liquid microextraction (DLLME) combined gas chromatography-electron capture detection (GC-ECD), for the determination of chlorobenzenes (CBs) in water samples, has been described. This method involves the use of an appropriate mixture of extraction solvent (9.5 μl chlorobenzene) and disperser solvent (0.50 ml acetone) for the formation of cloudy solution in 5.00 ml aqueous sample containing analytes. After extraction, phase separation was performed by centrifugation and the enriched analytes in sedimented phase were determined by gas chromatography-electron capture detection (GC-ECD). Our simple conditions were conducted at room temperature with no stiring and no salt addition in order to minimize sample preparation steps. Parameters such as the kind and volume of extraction solvent, the kind and volume of disperser solvent, extraction time and salt effect, were studied and optimized. The method exhibited enrichment factors and recoveries ranging from 711 to 813 and 71.1 to 81.3%, respectively, within very short extraction time. The linearity of the method ranged from 0.05 to 100 μg l⁻¹ for dichlorobenzene isomers (DCB), 0.002-20 μg l⁻¹ for trichlorobenzene (TCB) and tetrachlorobenzene (TeCB) isomers and from 0.001 to 4 μg l⁻¹ for pentachlorobenzene (PeCB) and hexachlorobenzene (HCB). The limit of detection was in the low μg l⁻¹ level, ranging between 0.0005 and 0.05 μg l⁻¹. The relative standard deviations (R.S.D.s) for the concentration of DCB isomers, 5.00 μg l⁻¹, TCB and TeCB isomers, 0.500 μg l⁻¹, PeCB and HCB 0.100 μg l⁻¹ in water by using the internal standard were in the range of 0.52-2.8% (n = 5) and without the internal standard were in the range of 4.6-6.0% (n = 5). The relative recoveries of spiked CBs at different levels of chlorobenzene isomers in tap, well and river water samples were 109-121%, 105-113% and 87-120%, respectively. It is concluded that this method can be successfully applied for the determination of CBs in tap, river and well water samples.     

Determination of four heterocyclic insecticides by ionic liquid dispersive liquid–liquid microextraction in water samples

A novel microextraction method termed ionic liquid dispersive liquid–liquid microextraction (IL-DLLME) combining high-performance liquid chromatography with diode array detection (HPLC-DAD) was developed for the determination of insecticides in water samples. Four heterocyclic insecticides (fipronil, chlorfenapyr, buprofezin, and hexythiazox) were selected as the model compounds for validating this new method. This technique combines extraction and concentration of the analytes into one step, and the ionic liquid was used instead of a volatile organic solvent as the extraction solvent. Several important parameters influencing the IL-DLLME extraction efficiency such as the volume of extraction solvent, the type and volume of disperser solvent, extraction time, centrifugation time, salt effect as well as acid addition were investigated. Under the optimized conditions, good enrichment factors (209–276) and accepted recoveries (79–110%) were obtained for the extraction of the target analytes in water samples. The calibration curves were linear with correlation coefficient ranged from 0.9947 to 0.9973 in the concentration level of 2–100 μg/L, and the relative standard deviations (RSDs, n = 5) were 4.5–10.7%. The limits of detection for the four insecticides were 0.53–1.28 μg/L at a signal-to-noise ratio (S/N) of 3.     

Dynamic supported liquid membrane tip extraction of glyphosate and aminomethylphosphonic acid followed by capillary electrophoresis with contactless conductivity detection

A dynamic supported liquid membrane tip extraction (SLMTE) procedure for the effective extraction and preconcentration of glyphosate (GLYP) and its metabolite aminomethylphosphonic acid (AMPA) in water has been investigated. The SLMTE procedure was performed in a semi-automated dynamic mode and demonstrated a greater performance against a static extraction. Several important extraction parameters such as donor phase pH, cationic carrier concentration, type of membrane solvent, type of acceptor stripping phase, agitation and extraction time were comprehensively optimized. A solution of Aliquat-336, a cationic carrier, in dihexyl ether was selected as the supported liquid incorporated into the membrane phase. Quantification of GLYP and AMPA was carried out using capillary electrophoresis with contactless conductivity detection. An electrolyte solution consisting of 12 mM histidine (His), 8 mM 2-(N-morpholino)ethanesulfonic acid (MES), 75 μM cetyltrimethylammonium bromide (CTAB), 3% methanol, pH 6.3, was used as running buffer. Under the optimum extraction conditions, the method showed good linearity in the range of 0.01–200 μg/L (GLYP) and 0.1–400 μg/L (AMPA), acceptable reproducibility (RSD 5–7%, n = 5), low limits of detection of 0.005 μg/L for GLYP and 0.06 μg/L for AMPA, and satisfactory relative recoveries (90–94%). Due to the low cost, the SLMTE device was disposed after each run which additionally eliminated the possibility of carry-over between runs. The validated method was tested for the analysis of both analytes in spiked tap water and river water with good success.     

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.     

Dispersive liquid-liquid microextraction followed by high-performance liquid chromatography as an efficient and sensitive technique for simultaneous determination of chloramphenicol and thiamphenicol in honey

Dispersive liquid-liquid microextraction (DLLME) coupled with high-performance liquid chromatography-variable wavelength detector (HPLC-VWD) was developed for extraction and determination of chloramphenicol (CAP) and thiamphenicol (THA) in honey. In this extraction method, 1.0 mL of acetonitrile (as dispersive solvent) containing 30 μL 1,1,2,2-tetrachloroethane (as extraction solution) was rapidly injected by syringe into a 5.00-mL water sample containing the analytes, thereby forming a cloudy solution. After extraction, phase separation was performed by centrifugation and the enriched analytes in the sedimented phase were determined by HPLC-VWD. Some important parameters, such as the nature and volume of extraction solvent and dispersive solvent, extraction time, sample solution pH, sample volume and salt effect were investigated and optimized. Under the optimum extraction condition, the method yields a linear calibration curve in the concentration range from 3 to 2000 μg kg⁻¹ for target analytes. The enrichment factors for CAP and THA were 68.2 and 87.9, and the limits of detection (S/N = 3) were 0.6 and 0.1 μg kg⁻¹, respectively. The relative standard deviations (RSDs) for the extraction of 10 μg kg⁻¹ of CAP and THA were 4.3% and 6.2% (n = 6). The main advantages of DLLME-HPLC method are simplicity of operation, rapidity, low cost, high enrichment factor, high recovery, good repeatability and extraction solvent volume at microliter level. Honey samples were successfully analyzed using the proposed method.     

Supramolecular solvent-based hollow fiber liquid phase microextraction of benzodiazepines

A new, efficient, and environmental friendly hollow fiber liquid phase microextraction (HF-LPME) method based on supramolecular solvents was developed for extraction of five benzodiazepine drugs. The supramolecular solvent was produced from coacervation of decanoic acid aqueous vesicles in the presence of tetrabutylammonium (Bu₄N⁺). In this work, benzodiazepines were extracted from aqueous samples into a supramolecular solvent impregnated in the wall pores and also filled inside the porous polypropylene hollow fiber membrane. The driving forces for the extraction were hydrophobic, hydrogen bonding, and π-cation interactions between the analytes and the vesicular aggregates. High-performance liquid chromatography with photodiode array detection (HPLC-DAD) was applied for separation and determination of the drugs. Several parameters affecting the extraction efficiency including pH, hollow fiber length, ionic strength, stirring rate, and extraction time were investigated and optimized. Under the optimal conditions, the preconcentration factors were obtained in the range of 112–198. Linearity of the method was determined to be in the range of 1.0–200.0 μg L⁻¹ for diazepam and 2.0–200.0 μg L⁻¹ for other analytes with coefficient of determination (R²) ranging from 0.9954 to 0.9993. The limits of detection for the target benzodiazepines were in the range of 0.5–0.7 μg L⁻¹. The method was successfully applied for extraction and determination of the drugs in water, fruit juice, plasma and urine samples and relative recoveries of the compounds studied were in the range of 90.0–98.8%.