Abstract
Five novel ionic liquids (ILs), 1,3-dibutylimidazolium bromide [BBMIm][Br], 1-pentyl-3-butylimidazolium bromide [BPMIm][Br], 1-hexyl-3-butylimidazolium bromide [BHMIm][Br], 1,1'-(butane-1,4-diyl)bis(3-butylimidazolium) bromide [C4(BMIm)2][Br2], and 1,1'-(butane-1,4-diyl)bis(3-methylimidazolium) bromide [C4(MIm)2][Br2], were prepared and used in situ to react with bis(trifluoromethane)sulfonamide lithium salt to extract the myclobutanil, tebuconazole, cyproconazole, and prothioconazole from water samples. The results showed that mono-cationic ILs had much better recovery than dicationic ILs, and mono-imidazolium IL bearing butyl groups at N-1 and N-3 sites had the best recovery. When the length of the alkyl substituent group was more than four carbons at N-3 site, the recovery decreased with increase of alkyl chain length of 1-butylimidazolium IL. The extraction efficiency order of triazoles from high to low was [BBMIm][Br], [BPMIm][Br], [BHMIm][Br], [BMIm][Br] (1-butyl-3-methylimidazolium bromide), [C4(BMIm)2]Br2, [C4(MIm)2]Br2. An in situ ionic liquid dispersive liquid–liquid microextraction combined with ultrasmall superparamagnetic Fe3O4 was established as a pretreatment method for enrichment of triazole fungicides in water samples by using the synthetic [BBMIm][Br] as the cationic IL and used to detect analytes followed by high-performance liquid chromatography. Under the optimized conditions, the proposed method showed a good linearity within a range of 5–250 μg L−1, with the determination coefficient (r2) varying from 0.998 to 0.999. High mean enrichment factors were achieved ranging from 187 to 323, and the recoveries of the target analytes from real water samples at spiking levels of 10.0, 20.0, and 50.0 μg L−1 were between 70.1% and 115.0%. The limits of detection for the analytes were 0.74–1.44 μg L−1, and the intra-day relative standard deviations varied from 5.23% to 8.65%. The proposed method can be further applied to analyze and monitor pesticides in other related samples.
Similar content being viewed by others
References
Kahle M, Buerge IJ, Hauser A, Muller MD, Poiger T. Azole fungicides: occurrence and fate in wastewater and surface waters. Environ Sci Technol. 2008;42(19):7193–200.
Price CL, Parker JE, Warrilow AG, Kelly DE, Kelly SL. Azole fungicides—understanding resistance mechanisms in agricultural fungal pathogens. Pest Manag Sci. 2015;71(8):1054–8.
Farajzadeh MA, Khoshmaram L. Air-assisted liquid-liquid microextraction-gas chromatography-flame ionisation detection: a fast and simple method for the assessment of triazole pesticides residues in surface water, cucumber, tomato and grape juices samples. Food Chem. 2013;141(3):1881–7.
Cui T, Zhang Y, Han W, Li J, Sun X, Shen J, et al. Advanced treatment of triazole fungicides discharged water in pilot scale by integrated system: Enhanced electrochemical oxidation, upflow biological aerated filter and electrodialysis. Chem Eng J. 2017;315:335–44.
Hu Y, Li J, Li G. Synthesis and application of a novel molecularly imprinted polymer-coated stir bar for microextraction of triazole fungicides in soil. J Sep Sci. 2011;34(10):1190–7.
Li Y, Zhang J, Peng B, Li S, Gao H, Zhou W. Determination of triazole pesticides in rat blood by the combination of ultrasound-enhanced temperature-controlled ionic liquid dispersive liquid–liquid microextraction coupled to high-performance liquid chromatography. Anal Methods. 2013;5(9):2241.
Wang H, Yang X, Hu L, Gao H, Lu R, Zhang S, et al. Detection of triazole pesticides in environmental water and juice samples using dispersive liquid-liquid microextraction with solidified sedimentary ionic liquids. New J Chem. 2016;40(5):4696–704.
Taxvig C, Hass U, Axelstad M, Dalgaard M, Boberg J, Andeasen HR, et al. Endocrine-disrupting activities in vivo of the fungicides tebuconazole and epoxiconazole. Toxicol Sci. 2007;100(2):464–73.
Paul Friedman K, Papineni S, Marty MS, Yi KD, Goetz AK, Rasoulpour RJ, et al. A predictive data-driven framework for endocrine prioritization: a triazole fungicide case study. Crit Rev Toxicol. 2016;46(9):785–833.
Jensen BH, Petersen A, Christiansen S, Boberg J, Axelstad M, Herrmann SS, et al. Probabilistic assessment of the cumulative dietary exposure of the population of Denmark to endocrine disrupting pesticides. Food Chem Toxicol. 2013;55:113–20.
EU. EU pesticide database. http://ec.europa.eu/food/plant/pesticides/max_residu_levels_en. Accessed 2016.
Güdücü HE, İnam R, Aboul-Enein HY. Determination of organophosphorus and triazole pesticides by gas chromatography and application to vegetable and commercial samples. J Liq Chromatogr Relat Technol. 2011;34(19):2473–83.
Farajzadeh MA, Mogaddam MR, Aghdam AA. Comparison of air-agitated liquid-liquid microextraction technique and conventional dispersive liquid-liquid micro-extraction for determination of triazole pesticides in aqueous samples by gas chromatography with flame ionization detection. J Chromatogr A. 2013;1300:70–8.
Wang C, Wu Q, Wu C, Wang Z. Application of dispersion-solidification liquid-liquid microextraction for the determination of triazole fungicides in environmental water samples by high-performance liquid chromatography. J Hazard Mater. 2011;185(1):71–6.
Wei Q, Song Z, Nie J, **a H, Chen F, Li Z, et al. Tablet-effervescence-assisted dissolved carbon flotation for the extraction of four triazole fungicides in water by gas chromatography with mass spectrometry. J Sep Sci. 2016;39(23):4603–9.
Tang T, Qian K, Shi T, Wang F, Li J, Cao Y. Determination of triazole fungicides in environmental water samples by high performance liquid chromatography with cloud point extraction using polyethylene glycol 600 monooleate. Anal Chim Acta. 2010;680(1-2):26–31.
Farajzadeh MA, Sorouraddin SM, Mogaddam MRA. Liquid phase microextraction of pesticides: a review on current methods. Microchim Acta. 2014;181(9-10):829–51.
Yang G, He Z, Liu X, Liu C, Zhan J, Liu D, et al. Polymer-coated magnetic nanospheres for preconcentration of organochlorine and pyrethroid pesticides prior to their determination by gas chromatography with electron capture detection. Microchim Acta. 2016;183(3):1187–94.
Yan H, Cheng X, Yan K. Rapid screening of five phthalate esters from beverages by ultrasound-assisted surfactant-enhanced emulsification microextraction coupled with gas chromatography. Analyst. 2012;137(20):4860–6.
Rezaee M, Assadi Y, Milani Hosseini MR, Aghaee E, Ahmadi F, Berijani S. Determination of organic compounds in water using dispersive liquid-liquid microextraction. J Chromatogr A. 2006;1116(1-2):1–9.
Rogers RD, Seddon KR. Chemistry. Ionic liquids–solvents of the future? Science. 2003;302(5646):792–3.
Jungnickel C, Łuczak J, Ranke J, Fernández JF, Müller A, Thöming J. Micelle formation of imidazolium ionic liquids in aqueous solution. Colloids Surf A Physicochem Eng Asp. 2008;316(1-3):278–84.
Reyna-Gonzalez JM, Torriero AA, Siriwardana AI, Burgar IM, Bond AM. Extraction of silver(I) from aqueous solutions in the absence and presence of copper(II) with a methimazole-based ionic liquid. Analyst. 2011;136(16):3314–22.
Zhou Q, Pang L, **ao J. Ultratrace determination of carbamate pesticides in water samples by temperature controlled ionic liquid dispersive liquid phase microextraction combined with high performance liquid phase chromatography. Microchim Acta. 2011;173(3-4):477–83.
Wang H, Hu L, Li W, Yang X, Lu R, Zhang S, et al. In-syringe dispersive liquid-liquid microextraction based on the solidification of ionic liquids for the determination of benzoylurea insecticides in water and tea beverage samples. Talanta. 2017;162:625–33.
Fan C, Liang Y, Dong H, Ding G, Zhang W, Tang G, et al. In-situ ionic liquid dispersive liquid-liquid microextraction using a new anion-exchange reagent combined Fe3O4 magnetic nanoparticles for determination of pyrethroid pesticides in water samples. Anal Chim Acta. 2017;975:20–9.
Shokri M, Beiraghi A, Seidi S. situ emulsification microextraction using a dicationic ionic liquid followed by magnetic assisted physisorption for determination of lead prior to micro-sampling flame atomic absorption spectrometry. Anal Chim Acta. 2015;889:123–9.
Lasarte-Aragones G, Lucena R, Cardenas S, Valcarcel M. Effervescence assisted dispersive liquid-liquid microextraction with extractant removal by magnetic nanoparticles. Anal Chim Acta. 2014;807:61–6.
Fan C, Li N, Cao X. Determination of chlorophenols in honey samples using in-situ ionic liquid-dispersive liquid-liquid microextraction as a pretreatment method followed by high-performance liquid chromatography. Food Chem. 2015;174:446–51.
Lopez-Darias J, Pino V, Ayala JH, Afonso AM. In-situ ionic liquid-dispersive liquid-liquid microextraction method to determine endocrine disrupting phenols in seawaters and industrial effluents. Microchim Acta. 2011;174(3-4):213–22.
Yao C, Li T, Twu P, Pitner WR, Anderson JL. Selective extraction of emerging contaminants from water samples by dispersive liquid-liquid microextraction using functionalized ionic liquids. J Chromatogr A. 2011;1218(12):1556–66.
Zhang C, Cagliero C, Pierson SA, Anderson JL. Rapid and sensitive analysis of polychlorinated biphenyls and acrylamide in food samples using ionic liquid-based in situ dispersive liquid-liquid microextraction coupled to headspace gas chromatography. J Chromatogr A. 2017;1481:1–11.
Konasova R, Dytrtova JJ, Kasicka V. Determination of acid dissociation constants of triazole fungicides by pressure assisted capillary electrophoresis. J Chromatogr A. 2015;1408:243–9.
EPA. Environmental Protection. Environmental quality standard of surface water: EPA; 2017. Chap. 61, p.11.
Turner NW, Subrahmanyam S, Piletsky SA. Analytical methods for determination of mycotoxins: a review. Anal Chim Acta. 2009;632(2):168–80.
Ojeda CB, Rojas FS. Separation and preconcentration by dispersive liquid–liquid microextraction procedure recent applications. Chromatographia. 2011;74(9-10):651–79.
Zhang Q, Tian M, Wang M, Shi H, Wang M. Simultaneous enantioselective determination of triazole fungicide flutriafol in vegetables, fruits, wheat, soil, and water by reversed-phase high-performance liquid chromatography. J Agric Food Chem. 2014;62(13):2809–15.
Acknowledgements
The authors acknowledge financial support of this work by the National Key Research and Development Program of China (2016YFF0203802) and the National Natural Science Foundation of China (31672067).
Author information
Authors and Affiliations
Corresponding author
Ethics declarations
Conflicts of interest
All authors of this article declare no conflict of interest.
Ethical Approval
This article does not contain any studies with human participants or animals performed by any of the authors.
Electronic supplementary material
ESM 1
(PDF 455 kb)
Rights and permissions
About this article
Cite this article
Yang, J., Fan, C., Kong, D. et al. Synthesis and application of imidazolium-based ionic liquids as extraction solvent for pretreatment of triazole fungicides in water samples. Anal Bioanal Chem 410, 1647–1656 (2018). https://doi.org/10.1007/s00216-017-0820-x
Received:
Revised:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s00216-017-0820-x