Determination of trichlorophenols in water samples by online pre-concentration method based on headspace in-tube microextraction-capillary electrophoresis

Document Type : Original Article

Author

Physics and Accelerators Research School, Nuclear Science & Technology Research Institute, P.O.BOX: 11365-3486., Tehran, Iran.

Abstract

In this study, a simple and efficient online preconcentration method based on headspace in-tube microextraction was used to simultaneously extract and preconcentrate small amounts of six trichlorophenols in aqueous samples. After extraction, the analytes were quantified by capillary electrophoresis and using the calibration curve of standard solutions. The effect of effective factors on the extraction process such as the pH of the donor phase, the type of the acceptor phase, the temperature and time of extraction, and the addition of organic solvent to the donor phase were investigated and optimized. Under optimal conditions, the linear dynamic range for the proposed technique was 15 to 1000 nM with a correlation coefficient of 0.99, and relative standard deviations were obtained with seven repetitions of the experiment and a concentration of 500 nM of analytes in the range of 4.78-7.63%. The detection limit of the method was 5-6 nM. The preconcentration factor for six trichlorophenols was obtained in the range of 310 to 661 times. Finally, this method was used to preconcentrate and measure six trichlorophenols in environmental water samples. The relative recoveries for the spiked samples were within the 82-92% range, indicating good accuracies and the absence of matrix effects.

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[1] Sharma N., Jain A., Singh V. K., Verma K. K. (2015) Solid-phase extraction combined with headspace single-drop microextraction of chlorophenols as their methyl ethers and analysis by high-performance liquid chromatography-diode array detection. Talanta, 83(3), 994-9.
[2] Li D., Oh J. R., Park J. (2003) Direct extraction of alkylphenols, chlorophenols and bisphenol A from acid-digested sediment suspension for simultaneous gas chromatographic–mass spectrometric analysis. J. Chromatogr. A, 1012(2), 207-214.
[3] Saraji M., Ghani M. (2015) Hollow fiber liquid–liquid–liquid microextraction followed by solid-phase microextraction and in situ derivatization for the determination of chlorophenols by gas chromatography-electron capture detection. J. Chromatogr. A, 1418, 45-53.
[4] Makuch B., Gazda K., Kamiski M. (1993) Determination of phenol and monochlorophenols in water by reversed-phase liquid chromatography. Anal. Chim. Acta, 284, 53-58.
[5] Crespin M. A., Gallego M., Valcarcel M. (2002) Solid-phase extraction method for the determination of free and conjugated phenol compounds in human urine. J. Chromatogr. B, 773(2), 89-96.
[6] Xiao Q., Hu B., Yu C., Xia L., Jiang Z. (2006) Optimization of a single-drop microextraction procedure for the determination of organophosphorus pesticides in water and fruit juice with gas chromatography-flame photometric detection. Talanta, 69 (4), 848-855.
[7] Mirzaei, N., Rezaei, V., Aibaghi, B. (2019). Preconcentration and determination of diazepam in pharmaceutical and biological samples by graphene oxide based on dispersive solid phase microextraction. Applied Chemistry, 14(51), 21-34. (in persion)
[8] Fathi, M., Rajabi, H. R., Khajehsharifi, H., Gorjizadeh Kohvadeh, A. Application of liquid-liquid microextraction based on deep eutectic solvent for preconcentration and spectrophotometric determination of purpurin. Applied Chemistry, (Articles in Press), (in persion), doi: 10.22075/CHEM.2023.28461.2107
 [9] Sorouraddin, S. M., Asadpour-Zeynali, K., Fathollahi, I. (2019). Development of a green dispersive liquid-liquid microextraction method using a home-made tablet disperser for extraction and preconcentration of Co (II) and Ni(II) from high volume aqueous samples. Applied Chemistry, 14(50), 139-154. (in persion)
[10] Bagheri H., Mir A., Babanezhad E. (2005) An electropolymerized aniline-based fiber coating for solid phase microextraction of phenols from water. Anal. Chim. Acta, 532, 89-95.
[11] Psillakis E., Kalogerakis N. (2003) Developments in liquid-phase Microextraction. Trends Anal. Chem, 22(10), 565-574.
[12] Helena P., Locita I. K. (1999) Solid-phase microextraction. Trends Anal. Chem, 18(4), 272-282.
[13] Lee H.R., Cho S.M., Kim J., Chung D.S. (2014) Novel and simple headspace in-tube microextraction coupled with capillary electrophoresis. J. Chromatogr. A, 1346, 117-122.
[14] Galan-Cano F., Lucena R., Cardenas S., Valcarcel M. (2012) Ionic liquid based in situ solvent formation microextraction coupled to thermal desorption for chlorophenols determination in waters by gas chromatography/mass spectrometry. J. Chromatogr. A, 1229, 48-54.
[15] Chien R.L., Burgi D. S. (1991) Field amplified sample injection in high-performance capillary electrophoresis. J. Chromatogr. A, 559(1–2), 141-152.
[16] Křivánková L., Pantůčková P., Boček P. (1999) Isotachophoresis in zone electrophoresis. J. Chromatogr. A, 838(1–2), 55-70.
[17] Park S. T., Kim J., Choi K., Lee H. R., Chung D. S. (2012) Headspace-single drop microextraction with a commercial capillary electrophoresis instrument. Electrophoresis, 33, 2961-2968.
[18] Es’haghi Z. (2011) Extraction and Determination of Three Chlorophenols by Hollow Fiber Liquid Phase Microextraction - Spectrophotometric Analysis, and Evaluation Procedures Using Mean Centering of Ratio Spectra Method. Am. J. Analyt. Chem, 2, 1-8.
[19] Lou D.-W., Lee X., Pawliszyn J. (2008) Extraction of formic and acetic acids from aqueous solution by dynamic headspace-needle trap extraction: Temperature and pH optimization. J. Chromatogr. A, 1201(2), 228-234.
 [20] Cho S.M., Park B.S., Jung W.S., Lee S.W., Jung Y., Chung D.S. (2016) Headspace in-tube microextraction coupled with micellar electrokinetic chromatography of neutral aromatic compounds. Talanta, 148, 729–733.
[21] George M. J., Marjanovic L., Williams D. B. G. (2015) Solvent-Assisted Headspace Sampling Using Solid Phase Microextraction for the Analysis of Phenols in Water. Anal. Chem, 87, 9559-9562.
[22] An Y., Ma W., Row K.H. (2020) Preconcentration and determination of chlorophenols in wastewater with dispersive liquid–liquid microextraction using hydrophobic deep eutectic solvents. Anal. Lett. 53, 262–272.
[23] Firouzy M., Hashemi P. (2023) Ionic Liquid-Based Magnetic Needle Headspace Single-Drop Microextraction Combined with HPLC/UV for the Determination of Chlorophenols in Wastewater. J. Chromatogr. Sci. 61, 743-749.
[24] Ma W., Row K.H. (2018) Solid-phase extraction of chlorophenols in seawater using a magnetic ionic liquid molecularly imprinted polymer with incorporated silicon dioxide as a sorbent. J. Chromatogr. A 1559, 78–85.
[25] Portillo M., Prohibas N., Salvadó V., Simonet B. (2006) Vial position in the determination of chlorophenols in water by solid phase microextraction. J. Chromatogr. A 1103, 29–34.
[26] Zhao L., Lee H.K. (2001) Determination of phenols in water using liquid phase microextraction with back extraction combined with high performance liquid chromatography. J. Chromatogr. A 931, 95–105.
[27] Gonzalez-Toledo E., Prat M., Alpendurada M. (2001) Solid-phase microextraction coupled to liquid chromatography for the analysis of phenolic compounds in water. J. Chromatogr. A 923, 45–52.