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Modified QuEChERS Method for Multiresidue Determination of Pesticides in Pecan Nuts by Liquid Chromatography Tandem Mass Spectrometry

Abstract

Pecan nut is a crop of growing economic importance with a worldwide production around 124,000 tons during the 2017/2018 harvest. Thus, a simple and fast method for the determination of pesticide residues in this crop based on a QuEChERS sample preparation procedure and liquid chromatography tandem mass spectrometry (LC-MS/MS) analysis was developed and validated. Despite the complexity of this matrix, with high fat content, the method was suitable to analyze 47 compounds in pecan nuts employing original QuEChERS salts and clean-up with the sorbents PSA and C18. This combination showed best results for lipid removal and compound recoveries when compared with the sorbents Z-Sep+, EMR-Lipid®, chitosan, diatomaceous earth, silica, and Florisil®. Validation was performed according to SANTE guideline using blank samples spiked at 5, 10, 20, 50, and 100 μg kg−1, and the proposed method presented satisfactory results with recoveries for most of the pesticides in the range of 70–120% with RSD < 20% and practical limits of quantification from 5 to 10 μg kg−1 for all compounds. The method was successfully applied in real samples and demonstrated to be simple, robust, and effective to be applied in routine analysis.

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References

  1. Anastas PT, Warner JC (1998) Green Chemistry: Theory and Practice, Oxford University Press: New York, p.30

  2. Agilent Technologies (2016) Enhanced Matrix Removal-Lipid Brochure. 5991-6052EN

  3. Anastassiades M, Lehotay S, Štajnbaher D, Schenck F (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 Intern 86:412–431

  4. Anastassiades M, Scherbaum E, Tasdelen B, Stajnbaher D (2007) Recent developments in QuEChERS methodology for pesticide multiresidue analysis. In: Ohkawa H, Miyagawa H, Lee PW (eds) Pesticide chemistry. Crop protection, public health, environmental safety. Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

  5. ANVISA (2019) Product regulation: agrochemical monographs, Brazilian health regulatory agency. < http://portal.anvisa.gov.br/registros-e-autorizacoes/agrotoxicos/produtos/monografia-de-agrotoxicos>

  6. Arias JLO, Rombaldi C, Caldas SS, Primel GE (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 1360:66–75

  7. Atanasov AG, Sabharanjakc SM, Zengind G, Mollicae A, Szostaka A, Simirgiotisg M, Huminieckia L, Horbanczukh OK, Nabavii SM, Mocanj A (2018) Pecan nuts: a review of reported bioactivities and health effects. Trends Food Sci Technol 71:246–257

  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 39:1945–1954

  9. de Matos EMC, Ribeiro LC, Prestes OD, da Silva JAG, de Farias BS, de A. Pinto LA, Zanella R (2019) Multiclass method for the determination of pesticide residues in oat using modified QuEChERS with alternative sorbent and liquid chromatography with tandem mass spectrometry. Food Anal Meth 12:2835–2844

  10. Donato FF, Martins ML, Munaretto SJ, Prestes OD, Adaime MB, Zanella R (2015) Development of a multiresidue method for pesticide analysis in drinking water by solid phase extraction and determination by gas and liquid chromatography with triple quadrupole tandem mass spectrometry. J Braz Chem Soc 26:2077–2087

  11. EFSA (2018) European Food Safety Authority. <http://www.efsa.europa.eu/en/topics/topic/pesticides>

  12. EURL-FV (2011) Determination of pesticide residues in avocado and almond by liquid and gas chromatography tandem mass spectrometry – European Union Reference Laboratory for Pesticide Residues

  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 1592:101–111

  14. INC (2018) Statistical Year Book for Nuts & Dried Fruits 2017/2018. <https://www.nutfruit.org/files/tech/1523960263_INC_Statistical_Yearbook_2017-2018.pdf>

  15. 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 8:728–739

  16. Khan Z, Kamble N, Bhongale A, Girme M, Bahadur Chauhan V, Banerjee K (2018) Analysis of pesticide residues in tuber crops using pressurised liquid extraction and gas chromatography-tandem mass spectrometry. Food Chem 241:250–257

  17. Kim L, Lee D, Cho HK, Choi SD (2019) Review of the QuEChERS method for the analysis of organic pollutants: Persistent organic pollutants, polycyclic aromatic hydrocarbons, and pharmaceuticals. Trends Environ Anal Chem 22:e00063

  18. Lee J, Kim L, Shin Y, Lee J, Lee J, Kim E, Moon J-K, Kim JH (2017) Rapid and simultaneous analysis of 360 pesticides in brown rice, spinach, orange, and potato using microbore GC-MS/MS. J Agric Food Chem 65:3387–3395

  19. Lee J, Shin Y, Lee J, Lee J, Kim BJ, Kim J-H (2018) Simultaneous analysis of 310 pesticide multiresidues using UHPLC-MS/MS in brown rice, orange, and spinach. Chemosphere 207:519–526

  20. Lehotay SJ, Mastovska K, Lightfield AR (2005) Use of bufferig 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 88:615–629

  21. Łozowicka B, Rutkowska E, Jankowska M (2017) Influence of QuEChERS modifications on recovery and matrix effect during the multi-residue pesticide analysis in soil by GC/MS/MS and GC/ECD/NPD. Environ Sci Pollut Res Int 24:7124–7138

  22. Martins GL, Friggi CA, Prestes OD, Vicari MC, Friggi DA, Adaime MB, Zanella R (2014) Simultaneous LC-MS/MS determination of imidazolinone herbicides together with other multiclass pesticide residues in soil. Clean Soil Air Water 42:1441–1449

  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 58:5959-5972

  24. Alvarez-Parrilla EA, Urrea-López RU, de la Rosa LA (2018) Bioactive components and health effects of pecan nuts and their by-products: a review. J Food Bioact 1:56–92

  25. Pavkovich AM, Bell DS (2018) QuEChERS. Encyclopedia of Analytical Science 3:1–6

  26. Perestrelo R, Silva P, Figueira PP, Pereira JAM, Silva C, Medina S, Câmara JS (2019) QuEChERS - Fundamentals, relevant improvements, applications and future trends. Anal Chim Acta 1070:1-28

  27. Prado ACP, Manion BA, Seetharaman K, Deschamps FC, Arellano DB, Block JM (2013) Relationship between antioxidant properties and chemical composition of the oil and the shell of pecan nuts [Caryaillinoinensis (Wangenh) C. Koch]. Ind Crop Prod 45:64–73

  28. Prestes DP, Adaime MB, Zanella R (2011) QuEChERS: possibilidades e tendências no preparo de amostra para determinação multirresíduo de pesticidas em alimentos. Scientia Chromatogr 3:51–64

  29. Rasche C, Fournes B, Dirks U, Speer K (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 1403:21–31

  30. SANTE (EUROPEAN COMMISSION) Guidance document on analytical quality control and method validation procedures for pesticides residues analysis in food and feed. Document SANTE/11813/2017

  31. Savant RH, Banerjee K, Utture SC, Patil SH, Dasgupta S, Ghaste MS, Adsule PG (2010) Multiresidue analysis of 50 pesticides in grape, pomegranate, and mango by gas chromatography-ion trap mass spectrometry. J Agric Food Chem 58:1447–1454

  32. The International Nut and Dried Fruit Council, INC (2018) Nut and Dried Fruit:Statistical Yearbook 2017-2018.

  33. Tsipi D, Botitsi H, Economou A (2015). Pesticide chemistry and risk assessment. Mass spectrometry for the analysis of pesticide residues and their metabolites, 1st, John Wiley & Sons

  34. Tuzimski T, Rejczak T (2016) Application of HPLC–DAD after SPE/QuEChERS with ZrO2-based sorbent in d-SPE clean-up step for pesticide analysis in edible oils. Food Chem 190:71–79

  35. Uclés A, López SH, Hermando MD, Rosal R, Ferrer C, Fernández-Alba (2015) Application of zirconium dioxide nanoparticle sorbent for the cleanup step in post-harvest pesticide residue analysis. Talanta 144:51-61

  36. USDA (2019) United States Department of Agriculture, National Nutrient Database for Standard Reference Legacy Release. <https://ndb.nal.usda.gov/ndb/foods/sho w/3645>

  37. Wang J, Gong Z, Zhang T, Feng S, Wang J, Zhang Y (2017) Simultaneous determination of 106 pesticides in nuts by LC-MS/MS using freeze-out combined with dispersive solid-phase extraction purification. J Sep Sci 40:2398–2405

  38. Zhang R, Peng F, Li Y (2015) Pecan production in China. Sci Hortic 197:719–727

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Acknowledgments

Particular words of gratitude are owed to Martha B. Adaime for her support and helpful comments.

Funding

This study was financed in part by the financial support and fellowships granted by the Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - Brasil (CAPES) - Finance Code 001 and CNPq.

Author information

Correspondence to Renato Zanella.

Ethics declarations

Conflict of Interest

Paulo E. P. Barci declares that he has no conflict of interest. Larissa da S. Alves declares that she has no conflict of interest. Állisson A. S. Avellar declares that he has no conflict of interest. Lucila R. Cendon declares that she has no conflict of interest. Pimpernelli J. dos Santos declares that she has no conflict of interest. Fabiane M. Stringhini declares that she has no conflict of interest. Osmar D. Prestes declares that he has no conflict of interest. Renato Zanella declares that he has no conflict of interest.

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

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Barci, P.E.P., Alves, L.d.S., Avellar, Á.A.S. et al. Modified QuEChERS Method for Multiresidue Determination of Pesticides in Pecan Nuts by Liquid Chromatography Tandem Mass Spectrometry. Food Anal. Methods 13, 793–801 (2020). https://doi.org/10.1007/s12161-019-01696-0

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Keywords

  • Pesticide residues
  • Sample preparation
  • Food
  • QuEChERS
  • LC-MS/MS