Magnetic Solvent Bar Liquid-Phase Microextraction Followed by Gas Chromatography-Flame Ionization Detection for the Trace Determination of Selected Polycyclic Aromatic Hydrocarbons in Environmental Water Samples


1 Research Institute of Petroleum Industry (RIPI), Tehran, Iran

2 Deptartment of Applied Chemistry, Faculty of Science, Islamic Azad University, South Tehran Branch, Tehran, Iran


A novel and efficient hollow fiber-based method, viz. magnetic solvent bar liquid-phase microextraction (MSB-LPME) combined with gas chromatography-flame ionization detection (GC-FID) was successfully developed for the trace determination of selected polycyclic aromatic hydrocarbons (PAHs) in environmental water samples. The target analytes were extracted from sample solution to the organic solvent immobilized in a fiber. After extraction, the analyte-adsorbed magnetic solvent bar could be readily isolated from the sample solution by a magnet which could greatly simplify the operation and also decline the total pretreatment time. The bar was first eluted with methanol, evaporated to dryness while the residue was dissolved in toluene and finally injected into GC-FID. Begin with, effective parameters controlling the performance of the microextraction were evaluated and optimized. The values of the detection limit of the method were in the range of 0.05-0.08 µg L-1 and the RSD% values for the analysis of 10.0 µg L-1 of the analytes was below than 5.8% (n= 6). A good linearity (0.998 ≥ r2 ≥ 0.994) and a broad linear range (0.1-200 µg L-1) were obtained. The method was eventually utilized for the preconcentration and determination of the PAHs in environmental water samples and satisfactory results were obtained.


  1. Santos F., Galceran M., 2002. The application of gas chromatography to environmental analysis. TrAC, Trends Anal Chem. 21(9), 672-685.
  2. Barro R., Regueiro J., Llompart M., Garcia-Jares C., 2009. Analysis of industrial contaminants in indoor air: Part 1. Volatile organic compounds, carbonyl compounds, polycyclic aromatic hydrocarbons and polychlorinated biphenyls. J Chromatogr A . 1216(3), 540-566.
  3. McIntosh A., Moffat C., Packer G., Webster L., 2004. Polycyclic aromatic hydrocarbon (PAH) concentration and composition determined in farmed blue mussels (Mytilus edulis) in a sea loch pre-and post-closure of an aluminium smelter. J Environ Monit. 6(3), 209-218.
  4. Ras M.R., Borrull F., Marcé R.M., 2009. Sampling and preconcentration techniques for determination of volatile organic compounds in air samples. TrAC, Trends Anal Chem. 28(3), 347-361.
  5. Shen H., 2016. Polycyclic Aromatic Hydrocarbons: Their Global Atmospheric Emissions, Transport, and Lung Cancer Risk. Springer
  6. Kleiböhmer, W., 2001. Environmental Analysis: Handbook of Analytical Separation.
  7. Hutzinger O., Beek B., Metzler M., 2013. The Handbook of Environmental Chemistry. Springer
  8. Zencak Z., Klanova J., Holoubek I., Gustafsson Ö., 2007. Source apportionment of atmospheric PAHs in the western Balkans by natural abundance radiocarbon analysis. Eniron Sci Technol. 41(11), 3850-3855.
  9. Wu H., Wang X., Liu B., Lu J., Du B., Zhang L., Ji J., Yue Q., Han B., 2010. Flow injection solid-phase extraction using multi-walled carbon nanotubes packed micro-column for the determination of polycyclic aromatic hydrocarbons in water by gas chromatographyââ‚‌“mass spectrometry. J Chromatogr A. 1217(17), 2911-2917.
  10. Sarafraz-Yazdi A., Amiri A., 2010. Liquid-phase microextraction. TrAC, Trends Anal Chem. 29(1), 1-14.
  11. Andraščíková M., Matisová E., Hrouzková S., 2015. Liquid phase microextraction techniques as a sample preparation step for analysis of pesticide residues in food.Sep Purif Rev. 44(1), 1-18.
  12. de la Calle I., Pena-Pereira F., Lavilla I., Bendicho C., 2016. Liquid-phase microextraction combined with graphite furnace atomic absorption spectrometry: A review. Anal Chim Acta. 936, 12-39.
  13. Rasmussen K.E., Pedersen-Bjergaard S., 2004. Developments in hollow fibre-based, liquid-phase microextraction. TrAC, Trends Anal Chem. 23(1), 1-10.
  14. Pedersen-Bjergaard S., Rasmussen K.E., 2008. Liquid-phase microextraction with porous hollow fibers, a miniaturized and highly flexible format for liquidââ‚‌“liquid extraction. J Chromatogr A. 1184(1), 132-142.
  15. Lee J., Lee H.K., Rasmussen K.E., Pedersen-Bjergaard S., 2008. Environmental and bioanalytical applications of hollow fiber membrane liquid-phase microextraction: a review. Anal Chim Acta. 624(2), 253-268.
  16. Bello-López M.Á., Ramos-Payán M., Ocaña-González J.A., Fernández-Torres R., Callejón-Mochón M., 2012. Analytical applications of hollow fiber liquid phase microextraction (HF-LPME): a review. Anal Lett 45(8), 804-830.
  17. Alsharif A.M.A., Tan G.H., Choo Y.M., Lawal A., 2017. Efficiency of Hollow Fiber Liquid-Phase Microextraction Chromatography Methods in the Separation of Organic Compounds: A Review. J Chromatogr Sci. 55(3), 378-391.
  18. Wu L., Song Y., Hu M., Zhang H., Yu A., Yu C., Ma Q., Wang Z., 2015. Application of magnetic solvent bar liquid-phase microextraction for determination of organophosphorus pesticides in fruit juice samples by gas chromatography mass spectrometry. Food Chem. 176, 197-204.
  19. Lambropoulou D.A., Albanis T.A., 2005. Application of hollow fiber liquid phase microextraction for the determination of insecticides in water. J Chromatogr A. 1072(1), 55-61.
  20. Zhao L., Lee H.K., 2002. Liquid-phase microextraction combined with hollow fiber as a sample preparation technique prior to gas chromatography/mass spectrometry. Anal Chem. 74(11), 2486-2492.
  21. Esââ‚‌™haghi Z., 2009. Determination of widely used non-steroidal anti-inflammatory drugs in water samples by in situ derivatization, continuous hollow fiber liquid-phase microextraction and gas chromatography-flame ionization detector. Anal Chim Acta. 641(1), 83-88.
  22. Abulhassani J., Manzoori J.L., Amjadi M., 2010. Hollow fiber based-liquid phase microextraction using ionic liquid solvent for preconcentration of lead and nickel from environmental and biological samples prior to determination by electrothermal atomic absorption spectrometry. J Hazard Mater. 176(1), 481-486.
  23. Farahani H., Shokouhi M., Rahimi-Nasrabadi M., Zare-Dorabei R., 2016. Green chemistry approach to analysis of formic acid and acetic acid in aquatic environment by headspace water-based liquid-phase microextraction and high-performance liquid chromatography. Toxicol Environ Chem. 98(7), 714-726.
  24. Zanjani M.R.K., Yamini Y., Shariati S., Jönsson J.Å., 2007. A new liquid-phase microextraction method based on solidification of floating organic drop. Anal Chim Acta. 585(2), 286-293.
  25. Han D., Row K.H., 2012. Trends in liquid-phase microextraction, and its application to environmental and biological samples. Microchim Acta. 176(1-2), 1-22.
  26. Gjelstad A., Jensen H., Rasmussen K.E., Pedersen-Bjergaard S., 2012. Kinetic aspects of hollow fiber liquid-phase microextraction and electromembrane extraction. Anal Chim Acta. 742, 10-16.
  27. Basheer C., Balasubramanian R., Lee H.K., 2003. Determination of organic micropollutants in rainwater using hollow fiber membrane/liquid-phase microextraction combined with gas chromatographyââ‚‌“mass spectrometry. J Chromatogr A. 1016(1), 11-20.
  28. Hou L., Lee H.K., 2002. Application of static and dynamic liquid-phase microextraction in the determination of polycyclic aromatic hydrocarbons. J Chromatogr A. 976(1-2), 377-385.
  29. Rezaee M., Assadi Y., Hosseini M.R.M., Aghaee E., Ahmadi F., Berijani S., 2006. Determination of organic compounds in water using dispersive liquidââ‚‌“liquid microextraction. J Chromatogr A. 1116(1-2), 1-9.
  30. Hosseini M.H., Rezaee M., Akbarian S., Mizani F., Pourjavid M.R., Arabieh M., 2013. Homogeneous liquidââ‚‌“liquid microextraction via flotation assistance for rapid and efficient determination of polycyclic aromatic hydrocarbons in water samples. Anal Chim Acta. 762, 54-60.