Hollow Fiber Based Liquid Phase Microextraction Method for the Determination of Three Triazine Herbicides from Locally Brewed Ethiopian Beverages

Document Type: Original research article


1 Department of Chemistry, Addis Ababa University, P. O. Box 1176, Addis Ababa, Ethiopia

2 1Department of Chemistry, Addis Ababa University, P. O. Box 1176, Addis Ababa, Ethiopia 2Department of Chemistry, College of Natural Sciences, Jimma University, P. O. Box 378, Jimma, Ethiopia


In this study, hollow-fiber based liquid-phase microextraction method was developed of for selective extraction and/or preconcentration of triazine herbicides (atratone, desmetryn and atrazine) from locally brewed Ethiopian beverages prior to their separation and quantitative determination by high performance liquid chromatography with diode array detector. Parameters influencing extraction efficiency of the method including types of the extraction solvent, volume and pH of the sample solution, shaking speed, extraction time and salt concentration were investigated and optimum conditions were established. Under the optimal conditions limits of detections and quantifications were ranged from 0.02 – 0.04 and 0.05 – 0.12 µg/L, respectively. Calibration curves were linear over the range of 0.1 – 2 µg/L with coefficient of determinations of 0.990 or better. Intra- and inter-day precision studies, which were expressed as relative standard deviations were below 8 %. Satisfactory relative recoveries were also obtained for the target analytes, except for atrazine in Nech Tela and Filter Tela, which exhibited relatively lower recoveries. The results of the study indicated that the proposed method is an efficient alternative for selective extraction and/or preconcentration of residues of the target pesticides form Ethiopian locally brewed beverages as well as other similar sample matrices.



[1]     H. Jiang, C. Adams, N.  Graziano, A. Roberson, M. McGuire and D. Khiari, Occurrence and removal of chloro-s-triazines in water treatment plants. Environ. Sci. Technol. 40 (2006) 3609–3616.

[2]     N. Papadopoulos, E. Gikas, G., Zalidis and A.Tsarbopoulos, Simultaneous determination of terbuthylazine and its major hydroxy and dealkylated metabolites in wetland water samples using solid-phase extraction and high-performance liquid chromatography with diode-array detection, J. Agric. Food Chem. 55 (2007) 7270−7277.

[3]     J. Peng, J. Lü, X. Hu, J. Liu and G. Jiang, Determination of atrazine, desethyl atrazine and desisopropyl atrazine in environmental water samples using hollow fiber-protected liquid-phase microextraction and high performance liquid chromatography, Microchim. Acta. 158 (2007) 181–186.

[4]     C. Chafer-Pericas, R. Herraez-Hernandez and P. Campins-Falco, On-fiber solid phase micro-extraction coupled to conventional liquid chromatography versus in tube solid-phase micro-extraction coupled to capillary liquid chromatography for the screening analysis of triazines in water samples, J. Chromatogr. A 1125 (2006) 159–171.

[5]     C. Wang, S. Ji, Q. Wu, C. Wu and Z. Wang, Determination of triazine herbicides in environmental samples by dispersive liquid-liquid microextraction coupled with high performance liquid chromatography, J. Chromatogr. Sci. 49 (2011) 689−694. 

[6]     M. Pirsaheb, N. Fattahi, M. Shamsipur and T. Khodadadi, Application of dispersive liquid-liquid microextraction based on solidification of floating organic drop for simultaneous determination of alachlor and atrazine in aqueous samples, J. Sep. Sci. 36 (2013) 684–689.

[7]     Regulation (EC) No. 396/2005 of the European parliament and of the council on maximum residue levels of pesticides in or on food and feed of plant and animal origin and amending Council Directive 91/414/EEC, Off. J. Eur. Commun. L70 (2005) 1–16.

[8]     Regulation (EC) No. 149/2008 amending Regulation (EC) No. 396/2005 of the European Parliament and of the Council by establishing Annexes II, III and IV setting maximum residue levels for products covered by Annex I thereto, Off. J. Eur. Commun. L58 (2008) 1–398.

[9]     US Environmental Protection Agency Office of Pesticide Programs: Index to pesticide chemical names, part 180 tolerance information, and food and feed commodities (by commodity), December 12, 2012

[10] Report of the Joint Meeting of the FAO Panel of Experts on Pesticide Residues in Food and the Environment and the WHO Core Assessment Group on Pesticide Residues Rome, Italy, 2016.

[11] P.C. Nascimento, A.L.B.  Rohlfes, D. Bohrer, L.M.  Carvalho and E.J. Pilau, HPLC based method using sample pre-column cleanup for the determination of triazines and thioltriazines in hemodialysis saline solutions, Talanta 65 (2005) 211–216.

[12] M.A.  Aramendîa, V. Borau, F. Lafont, A. Marinas, J. M. Marinas, J. M.  Moreno and F. Urbano, Determination of herbicide residues in olive oil by gas chromatography-tandem mass spectrometry, Food Chem. 105 (2007) 855–861.

[13] N. Megersa and S. Kassahun, A new selective liquid membrane extraction method for the determination of basic herbicides in agro-processed fruit juices and Ethiopian honey wine (Tej) samples, Food Addit. Contam. 29 (2012) 789–798.

[14] M.S. Dopico, M.V.  González, J.M.  Castro, E.  González, J.  Pérez, M.  Rodríguez and A. Calleja, Determination of triazines in water samples by high-performance liquid chromatography with diode-array detection, J. Chromatogr. Sci. 40 (2002) 523 - 528.

[15] A. Yohannes, T. Tolesa, Y. Merdassa  and N. Megersa, Single drop microextraction analytical technique for simultaneous separation and trace enrichment of atrazine and its major degradation products from environmental waters followed by liquid chromatographic determination, J. Anal. Bioanal. Tech. 7 (2016) 330. doi:10.4172/2155-9872.1000330

[16] D. Nagaraju and S. D. Huang, Determination of triazine herbicides in aqueous samples by dispersive liquid-liquid microextraction with gas chromatography-ion trap mass spectrometry, J. Chromatogr. A 1161 (2007) 89–97.

[17] T. Tolcha, Y. Merdassa Mand N. egersa, Low-density extraction solvent based solvent-terminated dispersive liquid-liquid microextraction for quantitative determination of ionizable pesticides in environmental waters, J. Sep. Sci. 36 (2013) 1119–1127.

[18] G. Shen and H. K. Lee, Hollow fiber-protected liquid-phase microextraction of triazine herbicides, Anal. Chem. 74 (2002) 648–654.

[19] N. Megersa, Hollow fiber-liquid phase microextraction for trace enrichment of the residues of atrazine and its major degradation products from environmental water and human urine samples, Anal. Methods 7 (2015) 9940–9948.

[20] Y. Hu, Y. Wang, Y. Hu and G. Li, Liquid-liquid-solid microextraction based on membrane-protected molecularly imprinted polymer fiber for trace analysis of triazines in complex aqueous samples, J. Chromatogr. A 1216 (2009) 8304–8311.

[21]  X. Hu, J. Liu, J. Å. Jönsson and G. Jiang, Development of negligible depletion hollow fiber-protected liquid-phase microextraction for sensing freely dissolved triazines, Environ. Toxicol. Chem. 28 (2009) 231–238.

[22] S. Pedersen-Bjergaard and K. E. Rasmussen, Liquid-phase microextraction with porous hollow fibers, a miniaturized and highly flexible format for liquid-liquid extraction, J. Chromatogr. A 1184 (2008) 132–142.

[23] M. Asensio-Ramos, L. M.  Ravelo-Pérez, M. A. González-Curbelo and J. Hernández-Borges, Liquid phase microextraction applications in food analysis, J. Chromatogr. A 1218 (2011) 7415–7437.

[24] D. Han and K. H.  Row, Trends in liquid-phase microextraction, and its application to environmental and biological samples, Microchim. Acta 176 (2012) 1–22.

[25] N. Megersa, T.  Solomon, B. S.  Chandravanshi and J. Å. Jonsson, Sample clean-up, enrichment and determination of triazine herbicides from southern Ethiopian lakes using supported liquid membrane extraction, Bull. Chem. Soc. Ethio. 14 (2000) 9–24.

[26] G. Tafere, A review on traditional fermented beverages of Ethiopian, J. Natural Sci. Res. 5 (2015) 94–102.

[27] M. Ashenafi, A review on the microbiology of indigenous fermented foods
and beverages of Ethiopia, Ethiop. J. Biol. Sci. 5 (2006) 189–245.

[28] M. Lee, M.  Regu and S. Seleshe, Uniqueness of Ethiopian traditional alcoholic beverage of plant origin, tella. J. Ethn Foods 2 (2015) 110–114.

[29] T. Yohannes, F. Melak and K. Siraj, Preparation and physicochemical analysis of some Ethiopian traditional alcoholic beverages, Afr. J. Food Sci. 7 (2013) 399-403.

[30] T. Berhanu, J.  Liu, R. Romero, N. Megersa, J. Å. Jönsson, Determination of trace levels of dinitrophenolic compounds in environmental water samples using hollow fiber supported liquid membrane extraction and high performance liquid chromatography, J. Chromatogr. A 1103 (2006) 1–8.

[31] J. Lee, H.K. Lee, K.E. Rasmussen and S. Pedersen-Bjergaard, Environmental and bioanalytical applications of hollow fiber membrane liquid-phase microextraction: a review,             Anal. Chim. acta 624 (2008) 253–268

[32] A. Gure, F.J. Lara, N. Megersa, A.M. García-Campaña and M. del Olmo-Iruela, Hollow fiber liquid phase microextraction combined with capillary HPLC for selective determination of six sulfonylurea herbicides in environmental waters, J. Sep. Sci. 36 (2013) 3395–3401.

[33] E. Carasek and J. Merib, Membrane-based microextraction techniques in analytical chemistry: a review, Anal. Chim. Acta. 880 (2015) 8–25.

[34] M. Michel. L. Chimuka, E. Cukrowska, P. Wieczorek and B. Buszewski, Influence of temperature on mass transfer in an incomplete trapping single hollow fiber supported liquid membrane extraction of triazole fungicides, Anal. Chim. Acta 632 (2009) 86–92.

[35] H.G. Ugland, M. Krogh and K.E. Rasmussen, Liquid phase micro-extraction as a sample preparation technique prior to capillary gas chromatographic-determination of benzodiazepines in biological matrices, J. Chromatogr. B 49 (2007) 85–92.

[36] S. P. Huang and S. D.  Huang, Determination of organochlorine pesticides in water using solvent cooling assisted dynamic hollow fiber supported headspace liquid phase micro-extraction, J. Chromatogr. A 1176 (2007) 19–25.

[37] L.J. Krutz, S.A. Senseman and A.S. Sciumbato, Solid-phase microextraction for herbicide determination in environmental samples, J. Chromatogr. A 999 (2003) 103–121.

[38] A.M.A. Alsharif, G.H. Tan, Y.M. Choo and A. Lawal, Efficiency of hollow fiber liquid-phase microextraction chromatography methods in the separation of organic compounds: a review, J. Chromatogr. Sci. 55 (2017) 378–391.

[39] M. Ghambarian, Y. Yamini and A. Esrafili, Developments in hollow fiber based liquid phase micro-extraction: principles and applications, Microchim. Acta 177 (2012) 271–294.

[40] C.M. Santana, Z.S. Ferrera, M.E.T. Padrón and J.J.S. Rodríguez, Methodologies for the extraction of phenolic compounds from environmental samples: new approaches, Molecules 14 (2009) 298–320.

[41] H. Ebrahimzadeh, Y. Yamini, H.A. Firozjaei, F. Kamarei, N. Tavassoli and M.R.  Rouini, Hollow fiber-based liquid phase microextraction combined with high-performance liquid chromatography for the analysis of gabapentin in biological samples, Anal. Chim. Acta 665 (2010) 221–226.

[42] Method validation and quality control procedures for pesticide residue analysis in food and feed, European Commission SANCO/10684/2009.

[43] J. Vessman, R.I. Stefan, J.F. van Staden, K. Danzer, W. Lindner, D. Burns, T. A. Fajgelj and H. Müller, Selectivity in analytical chemistry. Pure Appl. Chem. 37 (2001) 1381–1386.