Capillary electrophoresis determination of nonsteroidal anti‐inflammatory drugs in wastewater using hollow fiber liquid‐phase microextraction

The presence of pharmaceuticals in the environment due to growing worldwide consumption has become an important problem that requires analytical solutions. This paper describes a CE determination for several nonsteroidal anti‐inflammatory drugs (ibuprofen, naproxen, ketoprofen, diclofenac, ketorolac, aceclofenac and salicylic acid) in environmental waters using hollow fiber membrane liquid‐phase microextraction. The extraction was carried out using a polypropylene membrane supporting dihexyl ether and the electrophoretic separation was performed in acetate buffer (30 mM, pH 4) using ACN as the organic modifier. Detection limits between 0.25 and 0.86 ng/mL were obtained, respectively. The method could be applied to the direct determination of the seven anti‐inflammatories in wastewaters, and five of them have been determined or detected in different urban wastewaters.     

A three phase hollow fiber liquid‐phase microextraction for quantification of lamotrigine in plasma of epileptic patients by capillary electrophoresis

A three phase hollow fiber liquid‐phase microextraction technique combined with capillary electrophoresis was developed to quantify lamotrigine (LTG) in plasma samples. The analyte was extracted from 4.0 mL of a basic donor phase (composed of 0.5 mL of plasma and 3.5 mL of sodium phosphate solution pH 9.0) through a supported liquid membrane composed of 1‐octanol immobilized in the pores of the hollow fiber, and to an acidic acceptor phase (hydrochloric acid solution pH 4.0) placed in the lumen of the fiber. The extraction was carried out for 30 min at 500 rpm. The eletrophoretic analysis was carried out in 130 mmol/L MES buffer, pH 5.0 with a constant voltage of +15 kV and 20°C. Sample injections were performed for 10 s, at a pressure of 0.5 psi. The detection was performed at 214 nm for both LTG and the internal standard lidocaine. Under the optimized conditions, the method showed a limit of quantification of 1.0 μg/mL and was linear over the plasmatic concentration range of 1.0–20.0 μg/mL. Finally, the validated method was applied for the quantification of LTG in plasma samples of epileptic patients.     

Sensitive determination of chloroanilines in water samples by hollow fiber‐based liquid‐phase microextraction prior to capillary electrophoresis with amperometric detection

A hollow fiber‐based liquid‐phase microextraction method has been developed for enrichment of trace chloroanilines in water samples. Target analytes including aniline, three mono‐chlorinated aniline isomers (o‐chloroaniline, m‐chloroaniline, and p‐chloroaniline) and four mono‐chlorinated methylaniline isomers (2‐chloro‐4‐methylaniline, 3‐chloro‐4‐methylaniline, 4‐chloro‐2‐methylaniline, and 5‐chloro‐2‐methylaniline) were determined by CE with amperometric detection after microextraction. Several factors that affect separation, detection, and extraction efficiency were investigated. Under the optimum conditions, eight aniline compounds could be well separated from other components coexisting in water samples within 25 min, exhibiting a linear calibration over three orders of magnitude (r > 0.998); the obtained enrichment factors were between 51 and 239, and the LODs were in the range of 0.01–0.1 ng/mL. The proposed method has been applied for the analyses of real environmental water and sewage samples with relative recoveries in the range of 83–108%.     

Simultaneous extraction and quantification of albendazole and triclabendazole using vortex‐assisted hollow‐fiber liquid‐phase microextraction combined with high‐performance liquid chromatography

A novel, simple, and rapid vortex‐assisted hollow‐fiber liquid‐phase microextraction method was developed for the simultaneous extraction of albendazole and triclabendazole from various matrices before their determination by high‐performance liquid chromatography with fluorescence detection. Several factors influencing the microextraction efficiency including sample pH, nature and volume of extraction solvent, ionic strength, vortex time, and sample volume were investigated and optimized. Under the optimal conditions, the limits of detection were 0.08 and 0.12 μg/L for albendazole and triclabendazole, respectively. The calibration curves were linear in the concentration ranges of 0.3–50.0 and 0.4–50.0 μg/L with the coefficients of determination of 0.9999 and 0.9995 for albendazole and triclabendazole, respectively. The interday and intraday relative standard deviations for albendazole and triclabendazole at three concentration levels (1.0, 10.0, and 30.0 μg/L) were in the range of 6.0–11.0 and 5.0–7.9%, respectively. The developed method was successfully applied to determine albendazole and triclabendazole in water, milk, honey, and urine samples.     

Hollow fiber liquid‐phase microextraction and determination of nonsteroidal anti‐inflammatories by capillary electrophoresis and sulfonamides by HPLC in human urine

In this paper two applications of three‐phase HF‐LPME for the determination of pharmaceuticals in human urine are proposed: a capillary electrophoresis with a photodiode array detection method for the analysis of seven nonsteroidal anti‐inflammatory drugs (NSAIDs) and a high‐performance liquid chromatographic with photo diode array and fluorescence detection method for the determination of four sulfonamides and their corresponding N⁴‐acetyl‐metabolites. Q3/2 Accurel® polypropylene hollow fibers were used for both procedures. Dihexyl ether was used as the supported liquid membrane for the determination of anti‐inflammatories and 1‐octanol for sulfonamides. An aqueous solution (pH 12) was used in both procedures as the acceptor phase and as the donor phase an aqueous solution (pH 2), and a 2 m Na₂SO₄ aqueous solution (pH 4) was used for the determination of the anti‐inflammatories and sulfonamides. The detection limits obtained were between 0.25 (naproxen) and 0.86 ng/mL (aceclofenac) for the determination of anti‐inflammatories and 7 × 10^?4 (sulfamethoxazole) and 0.048 ng/mL (N⁴‐acetyl‐sulfamethazine) for sulfonamides. The method was successfully applied to the determination of the analytes in human urine. Copyright © 2012 John Wiley & Sons, Ltd.     

Hollow‐fiber liquid‐phase microextraction combined with capillary HPLC for the selective determination of six sulfonylurea herbicides in environmental waters

A three‐phase hollow‐fiber liquid‐phase microextraction combined with a capillary LC method using diode array detection was proposed for the determination of six sulfonylurea herbicides, triasulfuron, metsulfuron‐methyl, chlorsulfuron, flazasulfuron, chlorimuron‐ethyl, and primisulfuron‐methyl, in environmental water samples. Different factors that can affect the extraction process such as extraction solvent, acidity of the donor phase, composition and pH of the acceptor phase, salt addition, stirring speed, and extraction time were optimized. Under the optimum conditions, detection and quantitation limits between 0.1 – 1.7 and 0.3 – 5.7 μg/L, respectively, and enrichment factors ranging from 71 to 548 were obtained. The calibration curves were linear within the range of 0.3 – 40 μg/L. Intra‐ and interday RSDs were <6.3 and 8.4%, respectively. The relative recoveries of the spiked ground and river water samples were in the range of 69.4 – 119.2 and 77.4 – 111.7%, respectively. The results of the study revealed that the developed methodology involves an efficient sample pretreatment allowing the preconcentration of analytes, combined with the use of a miniaturized separation technique, suitable for the accurate determination of sulfonylurea herbicides in water.     

Stereoselective liquid chromatographic determination of 1'-oxobufuralol and 1'-hydroxybufuralol in rat liver microsomal fraction using hollow-fiber liquid-phase microextraction for sample preparation

A three-phase hollow-fiber liquid-phase microextraction (HF-LPME) method for the stereoselective determination of bufuralol metabolites 1'-oxobufuralol (1'-Oxo-BF) and 1'-hydroxybufuralol (1'-OH-BF) in microsomal preparations is described for the first time. The HPLC analysis was carried out using a Chiralcel OD-H column with hexane/2-propanol/methanol (97.5:2.0:0.5, v/v/v) plus 0.5% diethylamine as the mobile phase, and UV detection at 248 and 273 nm. The HF-LPME optimized conditions involved: n-octanol as the organic solvent, 0.2 mol/L acetic acid as the acceptor phase, donor phase pH adjusted to 13, sample agitation at 1500 rpm and extraction for 30 min. By using this extraction procedure, the recovery rates were in the range of 63-69%. The method was linear over the concentration range of 100-5000 ng/mL for each enantiomer of 1'-Oxo-BF (r>0.9978) and of 100-2500 ng/mL for each stereoisomer of 1'-OH-BF (r>0.9957). The quantification limits were 100 ng/mL for all analytes. The validated method was used to assess the in vitro biotransformation of bufuralol using rat liver microsomal fraction that demonstrated predominant formation of (S)-1'-Oxo-BF and (R,R)-1'-OH-BF.     

In situ derivatization and hollow‐fiber liquid‐phase microextraction to determine sulfonamides in water using UHPLC with fluorescence detection

A sensitive method for determining sulfonamides in water was developed and validated through in situ derivatization and hollow‐fiber liquid‐phase microextraction with ultra‐high performance liquid chromatography and fluorescence detection. The target sulfonamides were sulfadiazine, sulfacetamide, sulfamerazine, sulfamethazine, sulfamethoxypyridazine, sulfachloropyridazine, sulfamethoxazole, and sulfisoxazole. Following in situ derivatization with fluorescamine, three‐phase hollow‐fiber liquid‐phase microextraction with an S 6/2 polypropylene hollow‐fiber membrane was applied automatically using a multipurpose autosampler. Experimental parameters including derivatization time, choice of organic phase, pH of donor and acceptor phase, stirring rate, extraction temperature and time were optimized. Under optimized conditions, the target sulfonamides achieved excellent linearity with correlation coefficients of 0.9924–0.9994 within the concentration range of 0.05–5 μg/L. The limits of detection of the eight sulfonamides were 3.1–11.2 ng/L, and the limits of quantification were 10.3–37.3 ng/L. Enrichment factors of 0.1 and 5 μg/L sulfonamides spiked in lake water were 14–60, and recoveries were 56–113% with relative standard derivations of 3–19%. Applied with the developed method, sulfamerazine and sulfamethoxazole were measurable in both influent and effluent water of the three sewage treatment plants in Guangzhou, China. The developed method was sensitive and provided an alternative method for simultaneously enriching and quantifying multiple sulfonamides in environmental water.     

Three‐phase hollow‐fiber liquid‐phase microextraction based on deep eutectic solvent as acceptor phase for extraction and preconcentration of main active compounds in a traditional Chinese medicinal formula

A three‐phase hollow‐fiber liquid‐phase microextraction based on deep eutectic solvent as acceptor phase was developed and coupled with high‐performance capillary electrophoresis for the simultaneous extraction, enrichment, and determination of main active compounds (hesperidin, honokiol, shikonin, magnolol, emodin, and β,β′‐dimethylacrylshikonin) in a traditional Chinese medicinal formula. In this procedure, two hollow fibers, impregnated with n‐heptanol/n‐nonanol (7:3, v/v) mixture in wall pores as the extraction phase and a combination (9:1, v/v) of methyltrioctylammonium chloride/glycerol (1:3, n/n) and methanol in lumen as the acceptor phase, were immersed in the aqueous sample phase. The target analytes in the sample solution were first extracted through the organic phase, and further back‐extracted to the acceptor phase during the stirring process. Important extraction parameters such as types and composition of extraction solvent and deep eutectic solvent, sample phase pH, stirring rate, and extraction time were investigated and optimized. Under the optimal conditions, detection limits were 0.3–0.8 ng/mL with enrichment factors of 6–114 for the analytes and linearities of 0.001–13 μg/mL (r² ≥ 0.9901). The developed method was successfully applied to the simultaneous extraction and concentration of the main active compounds in a formula of Zi‐Cao‐Cheng‐Qi decoction with the major advantages of convenience, effectiveness, and environmentally friendliness.     

Bis(trifluoromethylsulfonyl)imide‐based frozen ionic liquid for the hollow‐fiber solid‐phase microextraction of dichlorodiphenyltrichloroethane and its main metabolites

1‐Hexadecyl‐3‐methylimidazolium bis(trifluoromethylsulfonyl)imide is a solid‐phase ionic organic material under ambient temperature and is considered as a kind of “frozen” ionic liquid. Because of their solid‐state and ultra‐hydrophobicity, “frozen” ionic liquids are able to be confined in the pores of hollow fiber, based on which a simple method was developed for the hollow‐fiber solid‐phase microextraction of dichlorodiphenyltrichloroethane and its main metabolites. Under optimized conditions, the proposed method results in good linearity (R ² > 0.9965) over the range of 0.5−50 μg/L, with low limits of detection and quantification in the range of 0.33−0.38 and 1.00−1.25 μg/L, respectively. Intra‐ and interday precisions evaluated by relative standard deviation were 3−6 and 1−6%, respectively. The spiked recoveries of dichlorodiphenyltrichloroethane and its main metabolites from real water samples were in the range of 64−113 and 79−112%, respectively, at two different concentration levels. The results suggest that “frozen” ionic liquids are promising for use as a class of novel sorbents.     

Ionic liquid‐based headspace in‐tube liquid‐phase microextraction coupled with CE for sensitive detection of phenols

An ionic liquid‐based headspace in‐tube liquid‐phase microextraction (IL‐HS‐ITLPME) in‐line coupled with CE is proposed. The method is capable of quantifying trace amounts of phenols in environmental water samples. In the newly developed method, simply by placing a capillary injected with ionic liquids (IL) in the HS above the aqueous sample, volatile phenols were extracted into the IL acceptor phase in the capillary. After extraction, electrophoresis of the phenols in the capillary was carried out. Extraction parameters such as the extraction time, extraction temperature, ionic strength, volume of the sample solution, and IL types were systematically investigated. Under the optimized conditions, enrichment factors for four phenols were from 1510 to 1985. The proposed method provided a good linearity, low limits of detection (below 5.0 ng/mL), and good repeatability of the extractions (RSDs below 6.7%, n = 6). This method was then utilized to analyze two real environmental samples of Xiaoxi Lake and tap water, obtaining acceptable recoveries and precisions. Compared with the usual HS‐ITLPME for CE, IL‐HS‐ITLPME‐CE is a simple, low cost, fast, and environmentally friendly preconcentration technique.     

Three‐phase hollow‐fiber liquid‐phase microextraction combined with HPLC–UV for the determination of isothiazolinone biocides in adhesives used for food packaging materials

The present study deals with the development of a liquid microextraction procedure for enhancing the sensitivity of the determination of 2‐methyl‐4‐isothiazolin‐3‐one and 5‐chloro‐2‐methyl‐4‐isothiazolin‐3‐one in adhesives. The procedure involves a three‐phase hollow‐fiber liquid‐phase microextraction using a semipermeable polypropylene membrane, which contained 1‐octanol as the organic phase in the pores of the membrane. The donor and acceptor phases are aqueous acidic and alkaline media, respectively, and the final liquid phase (acceptor) is analyzed by HPLC coupled with diode array detection. The most appropriate conditions were extraction time 20 min, stirring speed 1400 rpm, extraction temperature 50°C. The quantification limits of the method were 0.123 and 0.490 μg/g for 2‐methyl‐4‐isothiazolin‐3‐one and 5‐chloro‐2‐methyl‐4‐isothiazolin‐3‐one, respectively. Three different adhesive samples were successfully analyzed. The procedure was compared to direct analysis using ultra high pressure liquid chromatography coupled with TOF‐MS, where the identification of the compounds and the quantification values were confirmed.     

Development of hollow fiber‐supported liquid‐phase microextraction and HPLC‐DAD method for the determination of pyrethroid metabolites in human and rat urine

A simple hollow fiber liquid‐phase microextraction method for the determination of synthetic pyrethroid metabolites, 3‐phenoxybenzoic acid and 4‐hydroxy‐3‐phenoxybenzoic acid, in human and rat urine was developed and validated. A polypropylene hollow fiber tightly fitted onto a Nylon rod and impregnated with organic solvent served as a disposable extraction device. Desorption of analytes was carried out in NaOH solution, analyzed further by gradient HPLC and diode array detection method. Important factors were identified using Taguchi OA16 (4⁵) orthogonal array design and further optimized using univariate approach. The optimum method performance was observed when 1 mL of urine hydrolyzed with 0.2 mL of concentrated HCl was further supplemented with 100 mg of NaCl and extracted for 120 min into dihexyl ether immobilized in the pores of the hollow fiber. Metabolites were desorbed into 0.1 mL of 0.1 M NaOH for another 120 min. Limits of detection and quantitation of 15 and 50 ng/mL were obtained for both analytes. Relative standard deviations of 1.6–12.6% over the linear range (50–10,000 ng/mL, r > 0.9906) were observed. Intra‐ and inter‐day accuracies of the method ranged from 98.3 to 109.5% and from 93.3 to 110.9%, respectively. The optimized method was applied to the analysis of real urine samples collected from rats exposed orally to cypermethrin. Copyright © 2013 John Wiley & Sons, Ltd.     

Determination of partition coefficient and analysis of nitrophenols by three‐phase liquid‐phase microextraction coupled with capillary electrophoresis

A three‐phase hollow fiber liquid‐phase microextraction method coupled with CE was developed and used for the determination of partition coefficients and analysis of selected nitrophenols in water samples. The selected nitrophenols were extracted from 14 mL of aqueous solution (donor solution) with the pH adjusted to pH 3 into an organic phase (1‐octanol) immobilized in the pores of the hollow fiber and finally backextracted into 40.0 μL of the acceptor phase (NaOH) at pH 12.0 located inside the lumen of the hollow fiber. The extractions were carried out under the following optimum conditions: donor solution, 0.05 M H₃PO₄, pH 3.0; organic solvent, 1‐octanol; acceptor solution, 40 μL of 0.1 M NaOH, pH 12.0; agitation rate, 1050 rpm; extraction time, 15 min. Under optimized conditions, the calibration curves for the analytes were linear in the range of 0.05–0.30 mg/L with r²>0.9900 and LODs were in the range of 0.01–0.04 mg/L with RSDs of 1.25–2.32%. Excellent enrichment factors of up to 398‐folds were obtained. It was found that the partition coefficient (K_a/d) values were high for 2‐nitrophenol, 3‐nitrophenol, 4‐nitrophenol, 2,4‐dinitrophenol and 2,6‐dinitrophenol and that the individual partition coefficients (K_org/d and K_a/org) promoted efficient simultaneous extraction from the donor through the organic phase and further into the acceptor phase. The developed method was successfully applied for the analysis of water samples.     

Development of a novel hollow‐fiber liquid‐phase microextraction based on oil‐in‐salt and its comparison with conventional one

A novel hollow‐fiber liquid‐phase microextraction based on oil‐in‐salt was proposed and introduced for the simultaneous extraction and enrichment of the main active compounds of hesperidin, honokiol, shikonin, magnolol, emodin, and β,β′‐dimethylacrylshikonin in a formula of Zi‐Cao‐Cheng‐Qi decoction and the single herb, Fructus Aurantii Immaturus , Cortex Magnoliae Officinalis , Radix et Rhizoma , and Lithospermum erythrorhizon , composing the formula prior to their analysis by high‐performance liquid chromatography. The results obtained by the proposed procedure were compared with those obtained by conventional hollow‐fiber liquid‐phase microextraction, and the proposed procedure mechanism was described. In the procedure, a hollow‐fiber segment was first immersed in organic solvent to fill the solvent in the fiber lumen and wall pore, and then the fiber was again immersed into sodium chloride solution to cover a thin salt membrane on the fiber wall pore filling organic solvent. Under the optimum conditions, the enrichment factors of the analytes were 0.6–109.4, linearities were 0.002–12 μg/mL with r ² ≥ 0.9950, detection limits were 0.6–12 ng/mL, respectively. The results showed that oil‐in‐salt hollow‐fiber liquid‐phase microextraction is a simple and effective sample pretreatment procedure and suitable for the simultaneous extraction and concentration of trace‐level active compounds in traditional Chinese medicine.     

Hollow‐fiber liquid‐phase microextraction coupled with miniature capillary electrophoresis for the trace analysis of four aliphatic aldehydes in water samples

An environmentally friendly method for the trace analysis of four aliphatic aldehydes as water disinfection byproducts has been developed based on hollow‐fiber liquid‐phase microextraction followed by miniature capillary electrophoresis with amperometric detection. After derivatization with 2‐thiobarbituric acid, four aliphatic aldehydes (formaldehyde, acetaldehyde, propylaldehyde, and butyraldehyde) became detectable by the amperometric detector. Under the optimum conditions, four aliphatic aldehydes can be well separated from the coexisting interferents as well as their homologs (pentanal, glyoxal, and methyl‐glyoxal), and the limits of detection (S/N = 3) could reach sub‐nanogram‐per‐milliliter level based on hollow‐fiber liquid‐phase microextraction. The proposed method has been applied for the analyses of above four aliphatic aldehydes in different water samples such as drinking water, tap water, and river water, and the average recoveries were in the range of 90–113%, providing an alternative to conventional and microchip capillary electrophoresis approaches.     

Three‐phase hollow fiber liquid‐phase microextraction based on a magnetofluid for the analysis of aristolochic acids in plasma by high‐performance liquid chromatography

A new and fast sample preparation technique based on three‐phase hollow fiber liquid‐phase microextraction with a magnetofluid was developed and successfully used to quantify the aristolochic acid I (AA‐I) and AA‐II in plasma after oral administration of Caulis akebiae extract. Analysis was accomplished by reversed‐phase high‐performance liquid chromatography with fluorescence detection. Parameters that affect the hollow fiber liquid‐phase microextraction processes, such as the solvent type, pH of donor and acceptor phases, content of magnetofluid, salt content, stirring speed, hollow fiber length, extraction temperature, and extraction time, were investigated and optimized. Under the optimized conditions, the preconcentration factors for AA‐I and AA‐II were >627. The calibration curve for two AAs was linear in the range of 0.1–10 ng/mL with the correlation coefficients >0.9997. The intraday and interday precision was <5.71% and the LODs were 11 pg/mL for AA‐I and 13 pg/mL for AA‐II (S/N = 3). The separation and determination of the two AAs in plasma after oral administration of C. akebiae extract were completed by the validated method.     

Comparison of three‐phase hollow fiber liquid‐phase microextraction based on reverse micelle with conventional two‐phase hollow fiber liquid‐phase microextraction and their applications for analysis of cinnamic acids in traditional Chinese medicines

A novel three‐phase hollow fiber liquid‐phase microextraction was developed based on reverse micelle as extraction solvent and acceptor phase, and compared with conventional two‐phase hollow fiber liquid‐phase microextraction. Both procedures were used in the extraction and concentration of four cinnamic acids (caffeic acid, p‐hydroxycinnamic acid, ferulic acid, and cinnamic acid) in traditional Chinese medicines prior to high‐performance liquid chromatography analysis. Parameters affecting the two procedures were investigated and optimized to obtain the optimum enrichment factors. The mechanism of the developed procedure was explored and elucidated by comparison with conventional two‐phase hollow fiber liquid‐phase microextraction. Under the optimized conditions, the analytes’ enrichment factors were between 50 and 118 for the proposed procedure, and 31–96 for conventional two‐phase mode. Satisfactory linear ranges (r² ≥ 0.99), detection limits (0.1–0.6 ng/mL), precisions (<9.2%), and accuracies (recoveries: 80–123.1%) were observed for the two procedures. The results showed that the enrichment capacity of the proposed procedure for the cinnamic acids is better than that of conventional two‐phase procedure, and both are eco‐friendly, simple, and effective for the enrichment and detection of cinnamic acids in traditional Chinese medicines.     

Study of mass transfer in a dynamic hollow‐fibre liquid phase microextraction system

The extraction characteristics of a dynamic hollow‐fibre liquid phase microextraction system were investigated by studying the mass transfer and diffusion rates of dinitrophenols from plasma samples over the liquid membrane (dihexylether). The measured diffusion coefficients were compared with theoretical values calculated from Stokes diameters. The diffusion mechanism was simulated by computer and the most polar compounds, 2,4‐dinitrophenol and 4,6‐o‐dinitrocresol, had associated diffusion coefficients that were close to the calculated theoretical values. 2‐sec‐Butyl‐4,6 dinitrophenol and 2‐tert‐butyl‐4,6‐dinitrophenol, the compounds with the highest log P values, were retained by the polypropylene membrane, which reduced the experimentally observed diffusion rates to about half of the theoretical values. The retention was most likely due to dispersive forces interacting with the pore inner walls. Extraction was linearly correlated with time for all compounds and the repeatability was high (RSDs 7–11%), even for the shortest extraction times. Method LOD as the amount injected ranged between 0.3 and 3.1 ng for an extraction cycle of 213 s.     

Simultaneous speciation of inorganic chromium(III) and chromium(VI) by hollow‐fiber‐based liquid‐phase microextraction coupled with HPLC–UV

The speciation of chromium(VI) and chromium(III) was investigated by using hollow fiber liquid‐phase microextraction based on two immiscible organic solvents followed by high performance liquid chromatography with ultraviolet detection. In this method, chromium(VI) and chromium(III) reacted with ammonium pyrrolidine dithiocarbamate to produce hydrophobic complexes. Subsequently, the complexes were first extracted into a thin layer of organic solvent (n‐dodecane) present in the pores of a porous hollow fiber, and then into a μL volume of an organic acceptor (methanol) located inside the lumen of the hollow fiber. Then, the extracting organic phase was injected into the separation column of the high‐performance liquid chromatograph for the analysis of both chromium species. Effective parameters on extraction were optimized using one‐variable‐at‐a‐time method and central composite design. Under optimized conditions, a linear range of 0.25–100 and 0.5–100 μg/L (R ² > 0.998), the limits of detection of (S/N = 3) 0.08 and 0.1 μg/L and a preconcentration factor of 625 and 556 were achieved for chromium(VI) and chromium(III), respectively. The method was successfully applied to the speciation and determination of chromium species in different water samples and satisfactory results were obtained.