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Study of different HILIC, mixed-mode, and other aqueous normal-phase approaches for the liquid chromatography/mass spectrometry-based determination of challenging polar pesticides

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Abstract

The aim of the study was to evaluate the performance of different chromatographic approaches for the liquid chromatography/mass spectrometry (LC-MS(/MS)) determination of 24 highly polar pesticides. The studied compounds, which are in most cases unsuitable for conventional LC-MS(/MS) multiresidue methods were tested with nine different chromatographic conditions, including two different hydrophilic interaction liquid chromatography (HILIC) columns, two zwitterionic-type mixed-mode columns, three normal-phase columns operated in HILIC-mode (bare silica and two silica-based chemically bonded columns (cyano and amino)), and two standard reversed-phase C18 columns. Different sets of chromatographic parameters in positive (for 17 analytes) and negative ionization modes (for nine analytes) were examined. In order to compare the different approaches, a semi-quantitative classification was proposed, calculated as the percentage of an empirical performance value, which consisted of three main features: (i) capacity factor (k) to characterize analyte separation from the void, (ii) relative response factor, and (iii) peak shape based on analytes’ peak width. While no single method was able to provide appropriate detection of all the 24 studied species in a single run, the best suited approach for the compounds ionized in positive mode was based on a UHPLC HILIC column with 1.8 μm particle size, providing appropriate results for 22 out of the 24 species tested. In contrast, the detection of glyphosate and aminomethylphosphonic acid could only be achieved with a zwitterionic-type mixed-mode column, which proved to be suitable only for the pesticides detected in negative ion mode. Finally, the selected approach (UHPLC HILIC) was found to be useful for the determination of multiple pesticides in oranges using HILIC-ESI-MS/MS, with limits of quantitation in the low microgram per kilogram in most cases.

HILIC improves separation of multiclass polar pesticides

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Acknowledgments

The authors acknowledge funding from Junta de Andalucía through Research Project Ref. AGR-6182 and Research Group FQM323, and the Spanish Ministerio de Economía y Competitividad (MINECO) through Project Ref. CTQ-2015-71321, partially co-financed with FEDER funds. A.V. acknowledges the financial help to the Campus Hungary scholarship program (grant No. B1/1SZ/3704). J.R.M. also acknowledges funding from Plan Propio de Investigación of Universidad de Jaén (Ref. 2015/00018/001). B.G.L. acknowledges MINECO for her Juan de la Cierva postdoctoral research contract (ref. JCI-2012-12972).

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Authors and Affiliations

  1. Analytical Chemistry Research Group, Department of Physical and Analytical Chemistry, University of Jaén, Campus Las Lagunillas, 23071, Jaén, Spain

    Andrea Vass, José Robles-Molina, Patricia Pérez-Ortega, Antonio Molina-Díaz & Juan F. García-Reyes

  2. Department of Applied Chemistry, Faculty of Food Science, Szent István University, Villányi út 29-43, 1118, Budapest, Hungary

    Andrea Vass & Mihaly Dernovics

  3. Instituto de Investigación en Ciencias de la Alimentación, CIAL (CSIC-UAM), Nicolás Cabrera, 9, 28049, Madrid, Spain

    Bienvenida Gilbert-López

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  1. Andrea Vass
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  2. José Robles-Molina
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  3. Patricia Pérez-Ortega
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  4. Bienvenida Gilbert-López
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  5. Mihaly Dernovics
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  6. Antonio Molina-Díaz
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  7. Juan F. García-Reyes
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Correspondence to Juan F. García-Reyes.

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The research in this manuscript did not involve human participants and/or animals. All authors of this manuscript were informed and agreed for submission.

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The authors declare that they have no competing interests.

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Published in the topical collection featuring Young Investigators in Analytical and Bioanalytical Science with guest editors S. Daunert, A. Baeumner, S. Deo, J. Ruiz Encinar, and L. Zhang.

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Vass, A., Robles-Molina, J., Pérez-Ortega, P. et al. Study of different HILIC, mixed-mode, and other aqueous normal-phase approaches for the liquid chromatography/mass spectrometry-based determination of challenging polar pesticides. Anal Bioanal Chem 408, 4857–4869 (2016). https://doi.org/10.1007/s00216-016-9589-6

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  • DOI: https://doi.org/10.1007/s00216-016-9589-6

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