Residual Determination of Multiple Pesticides in Vegetable Samples by LC-MS/MS Coupled with Modified QuEChERS-dSPE Ionic Liquid-Based DLLME Method

Year 2021, Volume: 8 Issue: 2, 693 - 704, 31.05.2021

Abubakar Lawal , Kah Low

https://doi.org/10.18596/jotcsa.845578

Cited By: 3

Abstract

As a matter of fact, the Dietary Guidelines of the United States of America recommended the consumption of more fruits and vegetables to support the healthy condition of the body. Unfortunately, these food materials are being accumulated with pesticidal residues due to the continuous miss-management and excessive application of the chemicals during pre and post-agricultural practices, which compels multiple analysis of pesticidal residues to know their concentration levels for the betterment of food security and safety. For that matter, multi-residues of Thiamethoxam, Propamocarb, Carbaryl, Metalaxyl, Baycarb, Thiobencarb, Diazinon, and Dursban pesticides were determined in the samples of lettuce, garlic, ginger, and bell-pepper using modified QuEChERS-dSPE Ionic Liquid-based dispersive liquid-liquid microextraction (DLLME) method coupled with LC-MS/MS instrument and validated (European Union Guideline). Resultantly, the accuracy (87-127%) and precision (0–22%) were mostly within the acceptable range for the former (70-120%) and latter (≤20%). Meanwhile, the limit of detections (0.01-0.28 µg/kg) and limit of quantitations (0.03-0.93 µg/kg) were satisfactory. The concentration range (5–400 µg/kg) of calibration curves for the evaluated linearity were linear with coefficient of regressions greater than 0.99. The matrix effects for all the analyzed samples were very weak and less effective (≤ -86%). The range (1–25%) for the estimated measurement uncertainties were certifiable and acceptable (≤ 50%). Therefore, the sample preparation method prove effective as validated and useful for the multiple determination of pesticides residues in the analyzed vegetable samples, which are presumably safe for consumption against health issues.

Keywords

Pesticide residues, Fruits and vegetables, QuEChERS-dSPE and DLLME Cleanups, Ionic liquid-based, Liquid chromatography tandem mass spectrometry

Supporting Institution

University of Malaya Kuala Lumpur, Malaysia

Project Number

PG 174-2014B

Thanks

The Postgraduate Research Project (IPPP), University of Malaya Kuala Lumpur, Malaysia (PG 174-2014B) is acknowledged for the support rendered.

References

• 1. Lawal A, Koki IB. Determination of multi - pesticide residues in coconut water by QuEChERS - dSPE ionic liquid - based DLLME couple with high performance Liquid Chromatography - Tandem Mass Spectrometry (LCMS/MS). ChemSearch J. 2019;10(1):87–93. Url: https://www.ajol.info/index.php/csj/article/view/187964.
• 2. Koki IB, Lawal A, Taqui SN. Source identification and evaluation of surface water quality using factor and discriminant analysis. Bayero J Pure App Sci. 2019 May 9;11(2):169. Doi: https://doi.org/10.4314/bajopas.v11i2.21.
• 3. Baba A, Garba ST, Bello HS. Bioremediation Potential of Immobilized corynebacterium kutsceri in the Treatment of Tannery Industrial Effluent from Challawa Industrial Estate, Kano State, Nigeria. Journal of the Turkish Chemical Society Section A: Chemistry. 2020 Mar 30;335–50. Doi: https://doi.org/10.18596/jotcsa.643771.
• 4. Lawal A. Comparative analysis on selected bulb species. Sokoto, Nigeria: Usmanu Danfodiyo University. 2011;
• 5. Slavin JL, Lloyd B. Health Benefits of Fruits and Vegetables. Advances in Nutrition. 2012 Jul 1;3(4):506–16. Doi: https://doi.org/10.3945/an.112.002154.
• 6. Özer Z. Chemical Composition and Antioxidant Activities of Leaf and Flower Essential Oils of Origanum onites L. Growing in Mount Ida-Turkey. JOTCSA. 2020 Oct 30;7(3):813–20. Doi: https://doi.org/10.18596/jotcsa.780334.
• 7. Lattimer JM, Haub MD. Effects of Dietary Fiber and Its Components on Metabolic Health. Nutrients. 2010 Dec 15;2(12):1266–89. Doi: https://doi.org/10.3390/nu2121266.
• 8. Lawal A, Matazu S. Comparative Studies of White and Red Allium cepa Cultivated in Sokoto, Nigeria. ChemSearch J. 2015;6(2):14–20. Url: https://www.ajol.info/index.php/csj/article/view/130149.
• 9. Lawal A, Tan G, Alsharif A. Edibility and Medicinal Studies of Crinum ornatum inComparison with Allium sativum. Pakistan J Nutr. 2015;14(11):773–81.
• 10. Roth RA. Nutrition & diet therapy. Eleventh edition. Clifton Park, NY: Delmar Cengage Learning; 2014. 604 p. Isbn: 978-1-133-96050-8.
• 11. Kaiser KA, Brown AW, Bohan Brown MM, Shikany JM, Mattes RD, Allison DB. Increased fruit and vegetable intake has no discernible effect on weight loss: a systematic review and meta-analysis. The American Journal of Clinical Nutrition. 2014 Aug 1;100(2):567–76. Doi: https://doi.org/10.3945/ajcn.114.090548.
• 12. Esther G, Newark N. Dirt Poor: Have Fruits and Vegetables become Less Nutritious [Internet]. Scientific American; 2015. Available from: http://www.scientificamerican.com/article/soil-depletion-and-nutrition-loss/
• 13. Landsman J. The untold fruit and vegetable scandal [Internet]. Naturalhealth365.com; 2016. Available from: http://www.naturalhealth365.com/produce_scandal.html/
• 14. Kaur P, Bedi J, Sharma A, Gill J. Occurrence of Pesticide Residues in Water Collected from Different Water Sources in Punjab (India). Journal of Veterinary Public Health. 2016;12(2):75–9.
• 15. Lawal A, Wong RCS, Tan GH, Abdulra’uf LB, Alsharif AMA. Multi-pesticide Residues Determination in Samples of Fruits and Vegetables Using Chemometrics Approach to QuEChERS-dSPE Coupled with Ionic Liquid-Based DLLME and LC–MS/MS. Chromatographia. 2018 May;81(5):759–68. Doi: https://doi.org/10.1007/s10337-018-3511-7.
• 16. Lawal A, Abdulra’uf LB. Chemometrics Approach to QuEChERS-dSPE for Multi-Standard Determination of Pesticides in Blank Samples of Milli-Q-Water Using High-Performance Liquid Chromatography-Tandem Mass Spectrometry (LC-MS/MS). ChemSearch J. 2020;11(1):66–73. Url: https://www.ajol.info/index.php/csj/article/view/197383.
• 17. Erdoğan G, Yilmaz İ. Determination of Some Pesticides Harmful To Environment and Human Health in Bogazköy(Turkey) Dam Water by LC-MS/MS. JOTCSA. 2020 Oct 18;801–12. Doi: https://doi.org/10.18596/jotcsa.749021.
• 18. Zhang Y, Zhang Y, Nie J, Jiao B, Zhao Q. Determination of Triazole Fungicide Residues in Fruits by QuEChERS Combined with Ionic Liquid-Based Dispersive Liquid-Liquid Microextraction: Optimization Using Response Surface Methodology. Food Anal Methods. 2016 Dec;9(12):3509–19. Doi: https://doi.org/10.1007/s12161-016-0548-9.
• 19. Lawal A, Wong RCS, Tan GH, Abdulra’uf LB, Alsharif AMA. Recent Modifications and Validation of QuEChERS-dSPE Coupled to LC–MS and GC–MS Instruments for Determination of Pesticide/Agrochemical Residues in Fruits and Vegetables: Review. Journal of Chromatographic Science. 2018 Aug 1;56(7):656–69. Doi: https://doi.org/10.1093/chromsci/bmy032.
• 20. Lawal A, Tan GH, Alsharif AMA. Recent Advances in Analysis of Pesticides in Food and Drink Samples Using LPME Techniques Coupled to GC-MS and LC-MS: a Review. Journal of AOAC INTERNATIONAL. 2016 Nov 1;99(6):1383–94. Doi: https://doi.org/10.5740/jaoacint.16-0272.
• 21. Lawal A, Wong RCS, Tan GH, Abdulra’uf LB. Determination of Pesticide Residues in Fruit and Vegetables by High-Performance Liquid Chromatography–Tandem Mass Spectrometry with Multivariate Response Surface Methodology. Analytical Letters. 2019 Jan 22;52(2):231–48. Doi: https://doi.org/10.1080/00032719.2018.1459655.
• 22. Xie Q, Liu S, Fan Y, Sun J, Zhang X. Determination of phthalate esters in edible oils by use of QuEChERS coupled with ionic-liquid-based dispersive liquid–liquid microextraction before high-performance liquid chromatography. Anal Bioanal Chem. 2014 Jul;406(18):4563–9. Doi: https://doi.org/10.1007/s00216-014-7814-8.
• 23. Gunatilake SR, Kwon J-W, Mlsna TE, Xia K. A novel approach to determine estrogenic hormones in swine lagoon wastewater using the QuEChERS method combined with solid phase extraction and LC/MS/MS analysis. Anal Methods. 2014 Sep 23;6(23):9267–75. Doi: https://doi.org/10.1039/C4AY01804D.
• 24. Abdulra’uf LB, Tan GH. Chemometric approach to the optimization of HS-SPME/GC–MS for the determination of multiclass pesticide residues in fruits and vegetables. Food Chemistry. 2015 Jun;177:267–73. Doi: https://doi.org/10.1016/j.foodchem.2015.01.031.
• 25. Li M, Dai C, Wang F, Kong Z, He Y, Huang YT, et al. Chemometric-assisted QuEChERS extraction method for post-harvest pesticide determination in fruits and vegetables. Sci Rep. 2017 Mar;7(1):42489. Doi: https://doi.org/10.1038/srep42489.
• 26. SANTE-11813. Guidance document on analytical quality control and method validation procedures for pesticide residues and analysis in food and feed. European Commission; 2017.
• 27. Xiu-ping Z, Lin M, Lan-qi H, Jian-Bo C, Li Z. The optimization and establishment of QuEChERS-UPLC–MS/MS method for simultaneously detecting various kinds of pesticides residues in fruits and vegetables. Journal of Chromatography B. 2017 Aug;1060:281–90. Doi: https://doi.org/10.1016/j.jchromb.2017.06.008.
• 28. Kaczyński P. Large-scale multi-class herbicides analysis in oilseeds by rapid one-step QuEChERS-based extraction and cleanup method using liquid chromatography–tandem mass spectrometry. Food Chemistry. 2017 Sep;230:411–22. Doi: https://doi.org/10.1016/j.foodchem.2017.03.076.
• 29. Nantia EA, Moreno-González D, García-Campaña AM, Gámiz-Gracia L. High-Throughput Methodology for the Determination of Carbamates in Food Supplements by UHPLC–MS/MS. Chromatographia. 2017 Jan;80(1):63–70. Doi: https://doi.org/10.1007/s10337-016-3211-0.
• 30. Anonymous. Commission regulation. European Union; 2016.
• 31. Camino-Sánchez FJ, Zafra-Gómez A, Oliver-Rodríguez B, Ballesteros O, Navalón A, Crovetto G, et al. UNE-EN ISO/IEC 17025:2005-accredited method for the determination of pesticide residues in fruit and vegetable samples by LC-MS/MS. Food Additives & Contaminants: Part A. 2010 Nov;27(11):1532–44. Doi: https://doi.org/10.1080/19440049.2010.506602.
• 32. Lawal A. Experimental Designs of QuEChERS-Hexyl-Methylimidazolium Hexafluorophosphate Method Coupled With Liquid Chromatography-Mass Spectrometry for the Determination of Multiple Pesticides in Fruits and Vegetables [PhD THesis]. [Kuala Lumpur, Malaysia]: University of Malaya; 2018.