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Submitted
November 27, 2021
Accepted
December 29, 2021
Published
March 1, 2022
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Abstract

The analysis of polar herbicides by liquid chromatography-tandem mass spectrometry (LC-MS/MS) is challenging due to their complicated interactions. Diquat and paraquat, the bipyridilium group of polar herbicides, are widely used worldwide. This study aimed to optimize analytical conditions of diquat and paraquat in rice matrix using a hydrophilic interaction liquid chromatography column (Obelisc R; 2.1 x 150 mm, 5 µm). The mixtures of acetonitrile and ammonium formate buffer in water were used as mobile phase. All buffer solutions were acidified to a pH of 2.5 using concentrated formic acid. The results showed that 10 mM buffer concentration of ammonium formate was optimal compared to others, including 5, 20, and 50 mM. A mixture of methanol and water (6:4, v/v) containing 1% formic acid was used as an extractable solvent for sample preparation. Method quantitation limit (MQL) of diquat and paraquat in rice samples was 10 µg kg-1. Recoveries at different concentrations (i.e., 20, 50, and 100 µg kg-1) were higher than 70% for diquat, and 80% for paraquat with RSD < 20%, respectively. Diquat and paraquat in rice samples purchased from the local market were lower than MQL, with good recoveries for standard spiked samples.

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How to Cite
Nguyen, T.-N., Nguyen, C.-H., & Nguyen, N.-Q. (2022). Diquat and Paraquat Analysis in Rice using a Zwitterionic Hydrophilic Interaction Chromatography – tandem Mass Spectrometry. Indonesian Journal of Chemical Analysis (IJCA), 5(1), 29–40. https://doi.org/10.20885/ijca.vol5.iss1.art4
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References

  1. M. Pateiro-Moure, M. Arias-Estévez, and J. Simal-Gándara, "Critical Review on the Environmental Fate of Quaternary Ammonium Herbicides in Soils Devoted to Vineyards", Environmental Science & Technology, vol. 47 (10), pp. 4984-4998, 2013
  2. M. Pateiro-Moure, M. Arias-Estévez, E. López-Periago, E. Martínez-Carballo, and J. Simal-Gándara, "Occurrence and Downslope Mobilization of Quaternary Herbicide Residues in Vineyard-Devoted Soils", Bulletin of Environmental Contamination and Toxicology, vol. 80 (5), pp. 407-411, 2008
  3. D. I. Kolberg, D. Mack, M. Anastassiades, M. T. Hetmanski, R. J. Fussell, T. Meijer, and H. G. Mol, "Development and independent laboratory validation of a simple method for the determination of paraquat and diquat in potato, cereals and pulses", Anal Bioanal Chem, vol. 404 (8), pp. 2465-74, 2012.
  4. B. A. Bidlingmeyer, "Separation of ionic compounds by reversed-phase liquid chromatography an update of ion-pairing techniques", Journal of Chromatographic Science, vol. 18 (10), pp. 525-539, 1980.
  5. T. M. Chichila, and S. M. Walters, "Liquid chromatographic determination of paraquat and diquat in crops using a silica column with aqueous ionic mobile phase", Journal of the Association of Official Analytical Chemists, vol. 74 (6), pp. 961-967, 1991.
  6. M. A. Aramendía, V. Borau, F. Lafont, A. Marinas, J. M. Marinas, J. M. Moreno, J. M. Porras, and F. J. Urbano, "Determination of diquat and paraquat in olive oil by ion-pair liquid chromatography–electrospray ionization mass spectrometry (MRM)", Food Chemistry,vol. 97 (1), pp. 181-188, 2006.
  7. K. Andrew, and B. Adam, "Rapid Separation of Paraquat and Diquat Using Hydrophilic Interaction Chromatography (HILIC) with LC/MS Detection", Agilent, 2017.
  8. S. Y. Michael, and M. J. Kevin, "Oasis® WCX: A Novel Mixed-Mode SPE Sorbent for LC–MS Determination of Paraquat and Other Quaternary Ammonium Compounds", Waters, pp. 44-45, 2004.
  9. T. Zou, P. He, J. Cao, and Z. Li, "Determination of paraquat in vegetables using HPLC-MS-MS", J Chromatogr Sci, vol. 53 (2), pp. 204-9, 2015.
  10. P. G. Wang, and W. He, "Hydrophylic Interaction Liquid Chromatography and Advanced Applications". CPR Press Taylor & Francis Group. pp. 89, 2019.
  11. M. X. Chen, Z. Y. Cao, Y. Jiang, and Z. W. Zhu, "Direct determination of glyphosate and its major metabolite, aminomethylphosphonic acid, in fruits and vegetables by mixed-mode hydrophilic interaction/weak anion-exchange liquid chromatography coupled with electrospray tandem mass spectrometry", J Chromatogr A, vol. 1272, pp. 90-9, 2013
  12. I. R. Pizzutti, I. G. M. Vela, A. de Kok, J. M. Scholten, J. V. Dias, C.D. Cardoso, G. Concenço, and R. Vivian, "Determination of paraquat and diquat: LC-MS method optimization and validation", Food chemistry, vol. 209, pp. 248-255, 2016
  13. European Commission. List of pesticide MRLs. http://ec.europa.eu/food/plant/pesticides/eu-pesticides-database/public/?event=pesticide.residue.selection&language=EN (Access online 17 January, 2017).
  14. T. Axel and C. Ellanie, "Opportunities for Global Rice Research in a Changing World Technical bulletin Philippines". pp. 1, 2011.
  15. L. Pareja, A. R. Fernández-Alba, V. Cesio, and H. Heinzen, "Analytical methods for pesticide residues in rice", TrAC Trends in Analytical Chemistry, vol. 30 (2), pp. 270-291, 2011
  16. Technologies, SIELC. (Obelisc™ HPLC Columns - Liquid Separation Cell Technology, SIELC.
  17. M. Anastassiades, D. I. Kolberg, A. Benkenstein, E. Eichhorn, S. Zechmann, D. Mack, C. Wildgrube, I. Sigalov, D. Dörk, and A. Barth, "Quick method for the analysis of numerous highly polar pesticides in foods of plant origin via LC-MS/MS involving simultaneous extraction with methanol (QuPPe-method)", EU reference laboratory for pesticides requiring single residue methods (EURL-SRM). CVUA, Stuttgart, Germany, 2015.
  18. K. Wunnapuk, G. A. Medley, X. Liu, J. E. Grice, S. Jayasinghe, I. Gawarammana, N. A. Buckley, and M. S. Roberts, "Simple and sensitive liquid chromatography-tandem mass spectrometry methods for quantification of paraquat in plasma and urine: application to experimental and clinical toxicological studies", J Chromatogr B Analyt Technol Biomed Life Sci, vol. 879 (28), pp. 3047-52, 2011
  19. G. Greco, and T. Letzel, "Main interactions and influences of the chromatographic parameters in HILIC separations", J Chromatogr Sci, vol. 51 (7), pp. 684-93, 2013
  20. Y. Guo, and S. Gaiki, "Retention and selectivity of stationary phases for hydrophilic interaction chromatography", J Chromatogr A, vol. 1218 (35), pp. 5920-38, 2011
  21. J. Liigand, A. Laaniste, and A. Kruve, "pH Effects on Electrospray Ionization Efficiency", J Am Soc Mass Spectrom, vol. 28 (3), pp. 461-469, 2017