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Multiclass Method for the Determination of Pesticide Residues in Oat Using Modified QuEChERS with Alternative Sorbent and Liquid Chromatography with Tandem Mass Spectrometry

  • Estéfani M. C. de Matos
  • Lucila C. Ribeiro
  • Osmar D. Prestes
  • José A. G. da Silva
  • Bruna S. de Farias
  • Luiz A. de A. Pinto
  • Renato ZanellaEmail author
Article

Abstract

Many pesticides are used for pest control during oat production and storage, making necessary to employ multiclass methods for pesticide residue determination. In this work, an efficient QuEChERS method was established for multiresidue determination of 60 pesticides in oats by liquid chromatography with tandem mass spectrometry (LC-MS/MS). Different sorbents, such as chitosan, Forisil®, C18, PSA, Supel QuE Z-Sep+, and EMR-Lipid were evaluated for cleanup by dispersive solid-phase extraction (d-SPE). The original QuEChERS method had the best performance and the biosorbent chitosan presented similar results to the other conventional sorbents evaluated and being an efficient and low-cost biodegradable material was chosen for the cleanup step. The method presented adequate accuracy and precision using blank samples spiked between 5 and 100 μg kg−1, with recovery from 70 to 120% and RSD < 20% for all 60 pesticides and limits of quantification of 5 μg kg−1 for almost all studied pesticides, with exception of triflumizole for which was 10 μg kg−1. The method was successfully applied in real samples proven to be a good option for routine analysis. Oat samples presented residues of azoxystrobin, metalaxyl, and thiamethoxam.

Keywords

Pesticide residues Oat QuEChERS Chitosan LC-MS/MS 

Notes

Acknowledgments

The authors acknowledge the financial support and fellowships granted by the Brazilian agencies CNPq, CAPES, and FAPERGS.

Funding Information

This study was funded by the National Council of Scientific and Technological Development (CNPq), Brazil.

Compliance with Ethical Standards

Conflict of Interest

Estéfani M. C. de Matos declares that she has no conflict of interest. Fabiane M. Stringhini declares that she has no conflict of interest. Lucila C. Ribeiro declares that she has no conflict of interest. Osmar D. Prestes declares that he has no conflict of interest. José A. G. da Silva declares that he has no conflict of interest. Bruna S. de Farias declares that she has no conflict of interest. Luiz A. de A. Pinto declares that he has no conflict of interest. Renato Zanella declares that he has no conflict of interest.

Ethical Approval

This article does not contain any studies with human participants or animals performed by any of the authors.

Informed Consent

Informed consent was obtained from all individual participants included in the study.

Supplementary material

12161_2019_1641_MOESM1_ESM.docx (184 kb)
ESM 1 (DOCX 184 kb)

References

  1. Anastassiades M, Lehotay SJ, Stajnbaher D, Schenck FJ (2003) Fast and easy multiresidue method employing acetonitrile extraction/partitioning and dispersive solid phase extraction for the determination of pesticide residues in produce. J AOAC Int 86:412–431Google Scholar
  2. Anastassiades M, Scherbaum E, Taşdelen B, Šajnbaher D (2007) In: Ohkawa H, Miyagawa H, Lee PW (eds) Pesticide chemistry: crop protection, public health, environmental safety. Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim, pp 439–458CrossRefGoogle Scholar
  3. Arias JLO, Rombaldi C, Caldas SS, Primel EG (2014) Alternative sorbents for the dispersive solid-phase extraction step in quick, easy, cheap, effective, rugged and safe method for extraction of pesticides from rice paddy soils with determination by liquid chromatography tandem mass spectrometry. J Chromatogr A 1360:66–75CrossRefGoogle Scholar
  4. Arias JLO, Schneider A, Batista-Andrade JA, Vieira AA, Caldas SS, Primel EG (2018) Chitosan from shrimp shells: a renewable sorbent applied to the clean-up step of the QuEChERS method in order to determine multi-residues of veterinary drugs in different types of milk. Food Chem 240:1243–1253CrossRefGoogle Scholar
  5. Bauer A, Luetjohann J, Rohn S, Kuballa J, Jantzen E (2018) Development of an LC-MS/MS method for simultaneous determination of the quaternary ammonium herbicides Paraquat, Diquat, Chlormequat, and Mepiquat in plant-derived commodities. Food Anal Methods 11:2237–2243CrossRefGoogle Scholar
  6. Brazil (2012) Ministry of Agriculture, Livestock and Food Supply - Ordinance n° 325, of December 6, 2012Google Scholar
  7. Cabrera LC, Martins ML, Primel EG, Prestes OD, Adaime MB, Zanella R (2012) Dispersive solid phase extraction in the determination of residues and contaminants in food. Scientia Chromatographica 4:227–240CrossRefGoogle Scholar
  8. Cabrera LC, Caldas SS, Prestes OD, Primel EG, Zanella R (2016) Evaluation of alternative sorbents for dispersive solid-phase extraction clean-up in the QuEChERS method for the determination of pesticide residues in rice by liquid chromatography with tandem mass spectrometry. J Sep Sci 39:1945–1954CrossRefGoogle Scholar
  9. De Mori C, Fontaneli RS, Santos HP (2012) Economic and conjunctural aspects of oat culture. Documents Online 136. https://ainfo.cnptia.embrapa.br/digital/bitstream/item/91354/1/2013-documentosonline-136.pdf. Accessed 15 Jan 2019
  10. Dors GC, Primel EG, Fagundes CAA, Mariot CHP, Badiale Furlong E (2011) Distribution of pesticide residues in rice grain and in its coproducts. J Braz Chem Soc 22:1921–1930CrossRefGoogle Scholar
  11. EU Commission Regulation No 600/2010. https://eur-lex.europa.eu/LexUriServ/LexUriServ.do?uri=OJ:L:2010:174:0018:0039:EN:PDF Accessed 15 Jan 2019
  12. Facco JF, Martins ML, Bernardi G, Prestes OD, Adaime MB, Zanella R (2014) Optimization and validation of a multiresidue method for pesticide determination in maize using gas chromatography coupled to tandem mass spectrometry. Anal Methods 7:359–365CrossRefGoogle Scholar
  13. Francesquett JF, Rizzetti TM, Cadaval TRS Jr, Prestes OD, Adaime MB, Zanella R (2019) Simultaneous determination of the quaternary ammonium pesticides paraquat, diquat, chlormequat, and mepiquat in barley and wheat using a modified quick polar pesticides method, diluted standard addition calibration and hydrophilic interaction liquid chromatography coupled to tandem mass spectrometry. J Chromatogr A 1592:101–111CrossRefGoogle Scholar
  14. Gibney MJ et al (2009) Introduction to human nutrition, 2nd edn. Wiley-Blackwell, LondonGoogle Scholar
  15. Herrmann SS, Poulsen ME (2015) Clean-up of cereal extracts for gas chromatography–tandem quadrupole mass spectrometry pesticide residues analysis using primary secondary amine and C18. J Chromatogr A 1423:47–53CrossRefGoogle Scholar
  16. Kemmerich M, Rizzetti TM, Martins ML, Prestes OD, Adaime MB, Zanella R (2015) Optimization by central composite design of a modified QuEChERS method for extraction of pesticide multiresidue in sweet pepper and analysis by ultra-high-performance liquid chromatography-tandem mass spectrometry. Food Anal Methods 8:728–739CrossRefGoogle Scholar
  17. Koesukwiwat U, Lehotay SJ, Mastovska K, Dorweiler KJ, Leepipatpiboon N (2010) Extension of the QuEChERS method for pesticide residues in cereals to flaxseeds, peanuts and doughs. J Agric Food Chem 58:5950–5958CrossRefGoogle Scholar
  18. Lanças FM (2009) Modern liquid chromatography and mass spectrometry: finally “compatible”? Scientia Chromatographica 1:35–61Google Scholar
  19. Lehotay SJ, Mastovska K, Lightfield AR (2005) Use of buffering and other means to improve results of problematic pesticides in a fast and easy method for residue analysis of fruits and vegetables. J AOAC Intern 88:615–629Google Scholar
  20. Lucini L, Molinari GP (2011) Residues of pirimiphos-methyl in cereals and processed fractions following post-harvest spray application. J Environ Sci Health B 46:518–524CrossRefGoogle Scholar
  21. Martins GM, Toscano LC, Tomquelski GV, Maruyama WI (2009) Microbial insecticides and chemical in the control of fall armyworm on crop corn. Revista Caatinga 22:170–174Google Scholar
  22. Martins ML, Kemmerich M, Prestes OD, Maldaner L, Jardim ICSF, Zanella R (2017) Evaluation of an alternative fluorinated sorbent for dispersive solid-phase extraction clean-up of the quick, easy, cheap, effective, rugged, and safe method for pesticide residues analysis. J Chromatogr A 1514:36–43CrossRefGoogle Scholar
  23. Mastovska K, Dorweiler KJ, Lehotay SJ, Wegscheid JS, Szpylka KA (2010) Pesticide multiresidue analysis in cereal grains using modified QuEChERS method combined with automated direct sample introduction GC-TOFMS and UPLC-MS/MS techniques. J Agric Food Chem 58:5959–5972CrossRefGoogle Scholar
  24. May MM, Ferronato G, Bandeira NMG, Prestes OD, Zanella R, Adaime MB (2017) Determination of pesticide residues in soy-based beverages using a QuEChERS method (with clean-up optimized by central composite design) and ultra-high-performance liquid chromatography-tandem mass spectrometry. Food Anal Methods 10:369–378CrossRefGoogle Scholar
  25. Melo A, Cunha SC, Mansilha C, Aguiar A, Pinho O, Ferreira IMPLVO (2012) Monitoring pesticide residues in greenhouse tomato by combining acetonitrile-based extraction with dispersive liquid-liquid microextraction followed by gas-chromatography-mass spectrometry. Food Chem 135:1071–1077CrossRefGoogle Scholar
  26. Rasche C, Fournes B, Dirks U, Speer KN (2015) Multi-residue pesticide analysis (gas chromatography-tandem mass spectrometry detection)-improvement of the quick, easy, cheap, effective, rugged, and safe method for dried fruits and fat-rich cereals-benefit and limit of a standardized apple purée calibration (screening). J Chromatogr A 1403:21–31CrossRefGoogle Scholar
  27. Rekha NSN, Prasad R (2006) Pesticide residue in organic and conventional food-risk analysis. J Chem Health Saf 13:12–19CrossRefGoogle Scholar
  28. SANTE (European Commission) Guidance document on analytical quality control and method validation procedures for pesticides residues analysis in food and feed. Documento N° SANTE/11813/2017Google Scholar
  29. Santilio A, Stefanelli P, Girolimetti S, Dommarco R (2011) Determination of acidic herbicides in cereals by QuEChERS extraction and LC/MS/MS. J Environ Sci Health B 46:535–543Google Scholar
  30. Sterna V, Zute S, Brunava L (2016) Oat grain composition and its nutrition benefice. Agric Agric Sci Procedia 8:252–256Google Scholar
  31. Walorczyk S, Drożdżyński D (2012) Improvement and extension to new analytes of a multi-residue method for the determination of pesticides in cereals and dry animal feed using gas chromatography–tandem quadrupole mass spectrometry revisited. J Chromatogr A 1251:219–231CrossRefGoogle Scholar
  32. Wang H, Ding J, Ren N (2016) Recent advances in microwave-assisted extraction of trace organic pollutants from food and environmental samples. Trends Anal Chem 75:197–208CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media, LLC, part of Springer Nature 2019

Authors and Affiliations

  1. 1.Laboratory of Pesticide Residue Analysis (LARP), Chemistry DepartmentFederal University of Santa Maria (UFSM)Santa MariaBrazil
  2. 2.Regional University of Northwestern Rio Grande do Sul StateIjuíBrazil
  3. 3.School of Chemistry and FoodFederal University of Rio Grande (FURG)Rio GrandeBrazil

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