Skip to main content
SpringerLink
Log in

Advanced and Recent Approaches for Laboratory Methods of Pesticide Residues and Their Metabolites by Mass Spectrometry Techniques

  • Protocol
  • First Online:
Pesticide Toxicology

Part of the book series: Methods in Pharmacology and Toxicology ((MIPT))

  • 489 Accesses

Abstract

Several sectors like food safety, environmental exposure assessment, and lastly the biomonitoring have focused recently on the analysis of pesticide residues by mass spectrometric techniques. MS detectors such as ion trap, triple quadrupole, and quadrupole-linear ion trap tandem have made surprisingly good progress, largely as a result of the replacement of classical sample preparation by innovative, dynamic and modular dispersive solid-phase extraction (QuEChERS). The last years have seen a growing interest for QuEChERS approach, since fully miniaturizing sample preparation is technically possible, relatively cheap, and potentially of major benefit in terms of time of analysis. This approach is hugely versatile to provide good efficiency and robustness for target list of hundreds of compounds in several matrices. Moreover, introducing high-resolving power and mass accuracy has resolved complex analytical problems involved in untargeted and unknown pesticide analysis.

The MS ionization efficiency of analytes is usually influenced by matrix components. Changing MS conditions, optimizing chromatographic separations, and improving cleanups are basic strategies to minimize up to suppress the matrix effects. Several detection methods and compensation strategies of matrix effects are available, offering simple tools to mitigate the negative effects.

This is a preview of subscription content, log in via an institution to check access.

Access this chapter

Log in via an institution
Protocol
USD 49.95
Price excludes VAT (USA)
  • Available as PDF
  • Read on any device
  • Instant download
  • Own it forever
eBook
USD 99.00
Price excludes VAT (USA)
  • Available as EPUB and PDF
  • Read on any device
  • Instant download
  • Own it forever
Softcover Book
USD 129.99
Price excludes VAT (USA)
  • Compact, lightweight edition
  • Dispatched in 3 to 5 business days
  • Free shipping worldwide - see info
Hardcover Book
USD 199.99
Price excludes VAT (USA)
  • Durable hardcover edition
  • Dispatched in 3 to 5 business days
  • Free shipping worldwide - see info

Tax calculation will be finalised at checkout

Purchases are for personal use only

Institutional subscriptions

References

  1. Hassall KA (1982) The chemistry of pesticides: their metabolism, mode of action and uses in crop protection. Macmillan, London

    Google Scholar 

  2. Özkara A, Akyil D, Konuk M (2016) Pesticides, environmental pollution, and health. In: Environmental health risk-hazardous factors to living species. IntechOpen. https://doi.org/10.5772/63094

    Chapter  Google Scholar 

  3. Boobis AR, Ossendorp BC, Banasiak U, Hamey PY, Sebestyen I, Moretto A (2008) Cumulative risk assessment of pesticide residues in food. Tox Letters 180(2):137–150

    Article  CAS  Google Scholar 

  4. European Commission. Implementing Regulation (EU) 2019/533 of 28 March 2019 concerning a coordinated multiannual control programme of the Union for 2020, 2021 and 2022 to ensure compliance with maximum residue levels of pesticides and to assess the consumer exposure to pesticide residues in and on food of plant and animal origin. Official Journal L 88/28

    Google Scholar 

  5. U.S. Food and Drug Administration. Pesticide residue monitoring program fiscal year 2018 pesticide report. https://www.fda.gov/food/pesticides/pesticide-residue-monitoring-program-reports-and-data

  6. European Food Safety Authority (2015) Pesticide monitoring program: design assessment. EFSA J 13(2):4005, 1-52

    Google Scholar 

  7. European Parliament and Council. Regulation (EU) n. 625/2017 of the European Parliament and of the Council of 15 March 2017 on official controls and other official activities performed to ensure the application of food and feed law, rules on animal health and welfare, plant health and plant protection products. In: Official Journal of the European Union L95/1

    Google Scholar 

  8. European Council. Regulation (EC) No 396/2005 of the European Parliament and of the Council of 23 February 2005 on maximum residue levels of pesticides in or on food and feed of plant and animal origin and amending Council Directive 91/414/EEC. In: Official Journal of the European Union L70/1

    Google Scholar 

  9. Codex Alimentarius. Food and Agriculture Organization of the United Nations. World Health Organization. Maximum residue limits (MRLs) and risk management recommendations (RMRs) for residues of veterinary drugs in foods. www.codexalimentarius.org

  10. Bevan R, Brown T, Matthies F, Sams C, Jones K, Hanlon J, La Vedrine M (2017) Human biomonitoring data collection from occupational exposure to pesticides. External scientific report. European Food Safety Authority (EFSA)

    Google Scholar 

  11. European Food Safety Authority (2014) Guidance on the assessment of exposure of operators, workers, residents and bystanders in risk. EFSA J 12(10):3874

    Article  Google Scholar 

  12. Katsikantami I, Colosi C, Alegakis A, Tzatzarakis MN, Vakonaki E, Rizos AK, Sarigiannis DA, Tsatsakis AM (2019) Estimation of daily intake and risk assessment of organophosphorus pesticides based on biomonitoring data-the internal exposure approach. Food Chem Toxicol 123:57–71

    Article  CAS  Google Scholar 

  13. OECD (2018) Considerations for assessing the risks of combined exposure to multiple chemicals, series on testing and assessment N. 296. Environment, Health and Safety Division, Environment Directorate

    Book  Google Scholar 

  14. Food and Agriculture Organization of the United Nations (FAO) and World Health Organization (WHO) (2009) Principles and methods for the risk assessment of chemical in food. Environmental Health Criteria 240

    Google Scholar 

  15. U. S. Environmental Protection Agency (EPA). Environmental chemistry methods (ECM) and residue analytical methods (RAM). https://www.epa.gov/pesticide-analytical-methods. Accessed 22 Sept 2020

  16. European Standard. EN 15662: 2018 Foods of plant origin—Multimethod for the determination of pesticide residues using GC—and LC based analysis following acetonitrile extraction/partitioning and clean-up by dispersive SPE—Modular QuEChERS method

    Google Scholar 

  17. U. S. Food & Drug Administration (FDA). Pesticide Analytical Manual (PAM) https://www.fda.gov/food/laboratory-methods-food/pesticide-analytical-manual-pam. Accessed 22 Sept 2020

  18. European Union Reference Laboratory for pesticide residues. Single residue methods. https://www.eurl-pesticides.eu. Accessed 22 Sept 2020

  19. Paya P, Anastassiades M, Mack D, Sigalova I, Tasdelen B, Oliva J, Barba A (2007) Analysis of pesticide residues using the Quick Easy Cheap Effective Rugged and Safe (QuEChERS) pesticide multiresidue method in combination with gas and liquid chromatography and tandem mass spectrometric detection. Anal Bioanal Chem 389(6):1697–1714

    Article  CAS  Google Scholar 

  20. Anastassiades M, Lehotay SJ, Stajnbaher D, Schenck FJ (2003) Fast and easy multiresidue method employing acetonitrile extraction extraction/partitioning and “dispersive solid-phase extraction” for the determination of pesticide residue in produce. J AOAC Int 86(2):412–431

    Article  CAS  Google Scholar 

  21. Bruzzoniti MC, Checchini L, De Carlo RM, Orlandini S, Rivoira L, Del Bubba M (2014) QuEChERS sample preparation for the determination of pesticides and other organic residues in environmental matrices: a critical review. Anal Bioanal Chem 406:4089–4116

    Article  CAS  Google Scholar 

  22. Srivastava A, Rai S, Sonker AK, Karsauliya K, Pandey CP, Singh SP (2017) Simultaneous determination of multiclass pesticide residues in human plasma using a mini QuEChERS method. Anal Bioanal Chem 409:3757–3765

    Article  CAS  Google Scholar 

  23. Shin Y, Lee J, Park E, Lee J, Lee HS, Kim JH (2019) A quantitative tandem Mass spectrometry and scaled-down QuEChERS approach for simultaneous analysis of pesticide multiresidues in human urine. Molecules 24(7):1330. https://doi.org/10.3390/molecules24071330

    Article  CAS  PubMed Central  Google Scholar 

  24. Steinborn A, Alder L, Michalski B, Zomer P, Bending P, Martinez AS, Mol HGJ, Class TJ, Pinheiro NC (2016) Determination of glyphosate levels in breast milk samples from Germany by LC–MS/MS and GC–MS/MS. J Agric Food Chem 64:1414–1421. https://doi.org/10.1021/acs.jafc.5b05852

    Article  CAS  PubMed  Google Scholar 

  25. Santilio A, Stefanelli P, Dommarco R (2009) Fast determination of phenoxy acid herbicides in carrots and apples using liquid chromatography coupled triple quadrupole mass spectrometry. J Environ Sci Health B 44:584–590

    Article  CAS  Google Scholar 

  26. Stachniuk A, Fornal E (2016) Liquid chromatography-mass spectrometry in the analysis of pesticide residues in food. Food Anal Methods 9:1654–1665

    Article  Google Scholar 

  27. Stefanelli P, Generali T, Attard Barbini D, Girolimetti S (2019) A quick and inexpensive method to determine pesticide residues in olive oil by UHPLC-MS/MS and GC-MS/MS. Current Trends Anal Bioanal Chem 3(1):95–107

    Google Scholar 

  28. Kmellar B, Abranko L, Fodor P, Lehotay SJ (2010) Routine approach to qualitatively screening 300 pesticides and quantification of those frequently detected in fruit and vegetables using chromatography tandem mass spectrometry (LC–MS/MS). Food Addit Contam 27(10):1415–1430

    Article  CAS  Google Scholar 

  29. Hakme E, Lozano A, Ucles S, Fernandez-Alba AR (2018) Further improvements in pesticide residue analysis in food by applying gas chromatography triple quadrupole mass spectrometry (GC–QqQ–MS/MS) technologies. Anal Bioanal Chem 410:5491–5506

    Article  CAS  Google Scholar 

  30. Rajski L, Martinez-Bueno MJ, Ferrer C, Fernandez-Alba AR (2019) LC–ESI–QOrbitrap MS/MS within pesticide residue analysis in fruits and vegetables. Trends Anal Chem 118:587–596

    Article  CAS  Google Scholar 

  31. Rajski L, Beraza I, Gomez-Ramos MJ, Ferrer C, Fernandez-Alba AR (2020) Evaluation of segmented non-target data acquisition (SWATH/vDIA) in a QToF and QOrbitrap for pesticide residue analysis. Anal Methods 12:2027–2038

    Article  CAS  Google Scholar 

  32. EFSA. Oltmanns J, Bohen ML, Escher S, Schwarz M, Licht O (2019) Final report: applying a tested procedure for the identification of potential emetging chemical risks in the food chain to the substances registered under REACH–REACH 2. External scientific report. OC/EFSA/SCER/2016/01-CT1. EFSA J. https://doi.org/10.2903/sp.efsa.2019.EN-1597

  33. Oltmanns J, Licht O, Bohlen ML, Schwarz M, Escher SE, Silano V, Macleod M, Noteborn HPJM, Kass GEN, Merten C (2020) Environmental science: processes & impacts. Issue 1

    Google Scholar 

  34. Directorate General for Health and Consumer Affairs (2019) Method validation and quality control procedures for pesticide residues analysis in food and feed. In: Document SANTE/12682/2019 implemented by 01/01/2020. Brussels, Belgium

    Google Scholar 

  35. U.S FDA (2019) Guidelines for the validation of chemical methods in food, feed, cosmetics, and veterinary products. https://www.fda.gov

  36. Stanhnke H, Alder L (2015) Matrix effects in liquid chromatography—electrospray ionization—mass spectrometry. In: Mass spectrometry for the analysis of pesticide residues and their metabolites. Wiley, Hoboken, NJ

    Google Scholar 

  37. Fujiyoshi T, Ikami T, Yamamoto A (2016) Evaluation of the matrix effect on gas chromatography – mass spectrometry with carrier gas containing ethylene glycol as an analyte protectant. J Chromatogr A 1434:136–141. https://doi.org/10.1016/j.chroma.2015.12.085

    Article  CAS  PubMed  Google Scholar 

  38. Kruve A, Leito I (2013) Comparison of different methods aiming to account for/overcome matrix effects in LC/ESI/MS on the example of pesticide analyses. Anal Methods 5(12):3035–3044. https://doi.org/10.1039/c3ay26551j

    Article  CAS  Google Scholar 

  39. Zhang Q, Yang Y, Liu X, Chen Y, Hu D, Lu P (2019) Simultaneous determination of Flonicamid and its metabolites in tea by liquid chromatography tandem mass spectrometry. Anal Lett 52(6):948–961. https://doi.org/10.1080/00032719.2018.1508294

    Article  CAS  Google Scholar 

  40. Sannani P, Viskwakarma K, Saha BB (2015) Optimization of extraction techniques SPE, QuEChERS and ultrasound method for trace level determination of Imidacloprid in vegetables (cabbage and spinach) and soil by UPLC. Int J Anal Tech 1(1):1. https://doi.org/10.15226/2471-3627/1/1/00101

    Article  Google Scholar 

  41. Anastassiades M, Kolberg DI, Eichhorn A, Wachtler K, Benkenstein A, Zechmann S, Mack D, Wildgrube C, Barth A, Sigalov I, Gorlich S, Dörk D, Cerchia G. Quick method for the analysis of numerous highly polar pesticides in food involving extraction with acidified methanol and LC-MS/MS measurement. QuPPe–PO-Method version 11 updated 12.02.2020. QuPPe–AO-Method version 3.2 updated 14.05.2019. https://www.eurl-pesticides.com

  42. Roca M, Leon N, Yusà V (2014) Comprehensive analytical strategy for biomonitoring of pesticides in urine by liquid chromatography–orbitrap high resolution mass spectrometry. J Chromatogr A 1374:66–76

    Article  CAS  Google Scholar 

  43. Stefanelli P, Attard Barbini D, Girolimetti S (2021) Pesticides and their metabolites in human urine: development of multi-analyte method by LC-MS/MS and GC-MS/MS. J Environ Sci Health B 56(5):431–438. https://doi.org/10.1080/03601234.2021.1894887

    Article  CAS  PubMed  Google Scholar 

  44. Macedo AN, Nogueira ARA, Govoni Brondi SH (2009) Matrix solid phase dispersion extraction for analysis of cypermethrin residue in cow’s milk. Chromatographia 69:571–573

    Article  CAS  Google Scholar 

  45. Jansen HG, Marriott PJ, Vreuls RJJ (2006) Trends and Developments in gas chromatography. J Chromatogr Gas Chromatogr 1186(1–2):1–440

    Google Scholar 

  46. Hertherton C, Sykes M, Fussell R, Goodall DM (2004) A multi-residue screening method for the determination of 73 pesticides and metabolites in fruit and vegetables using high-performance liquid chromatography/tandem mass spectrometry. Rapid Commun Mass Spectrom 18(20):2443–2450

    Article  Google Scholar 

  47. Makarov A, Denisov E, Kholomeev A, Balschun W, Lange O, Strupat K, Horning S (2006) Performance evaluation of a hybrid linear Ion Trap/Orbitrap mass spectrometry. Anal Chem 78:2113–2120

    Article  CAS  Google Scholar 

  48. European Commission. EU reference laboratories for residues of pesticides. EURL–DataPool. https://eurl-pesticides-datapool.eu (v1.8.311.1 7/31/2020)

  49. Gomez-Ramos MJ, Ferrer C, Malato O, Aguera A, Fernandez-Alba AR (2013) Liquid chromatography-high-resolution mass spectrometry for pesticide residue analysis in fruit and vegetables: screening and quantitative studies. J Chromatogr A 1287:24–37

    Article  CAS  Google Scholar 

  50. Vass A, Robles-Molina J, Pérez Ortega P, Gilbert López B (2016) 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

    Article  CAS  Google Scholar 

  51. Thompson M, Ellison SLR, Wood R (2002) IUPAC technical report. Harmonized guidelines for single laboratory validation of methods of analysis. Pure Appl Chem 74:835–855

    Article  CAS  Google Scholar 

  52. Mol HGJ, Zomer P, Garcia Lopez M, Fussel RJ, Scholten J, de Kok A, Wolheim A, Anastassiades M, Lozano A, Fernandez Alba A (2015) Identification in residue analysis based on liquid chromatography with tandem mass spectrometry: experimantal evidence to update performance criteria. Anal Chim Acta 873:1–13

    Article  CAS  Google Scholar 

  53. EURACHEM (2011) Selection, use and interpretation of proficiency testing (PT) schemes, 2nd edn

    Google Scholar 

  54. Kwon H, Lehotay SJ, Asteggiante LG (2012) Variability of matrix effects in liquid and gas chromatography-mass spectrometry analysis of pesticide residues after QuEChERS sample preparation of different food crops. J Chromatogr A 1270:235–245

    Article  CAS  Google Scholar 

  55. Hajslowa J, Zrostíkova J (2003) Matrix effects in (ultra)trace analysis of pesticide residues in food and biotic matrices. J Chromatogr A 1000:181–197

    Article  Google Scholar 

  56. Chawla S, Patel HK, Gor HN, Vaghela KM, Solanki PP, Shah PG (2017) Evaluation of matrix effects in multiresidue analysis of pesticide residues in vegetable and spices by LC–MS/MS. J AOAC Int 100(3):616–623

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Exposure to Air, Soil and Lifestyle Contaminants Unit, Environment and Health Department, Istituto Superiore di Sanità (National Institute of Health), Rome, Italy

    Patrizia Stefanelli & Danilo Attard Barbini

Authors
  1. Patrizia Stefanelli
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Danilo Attard Barbini
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Patrizia Stefanelli .

Editor information

Editors and Affiliations

  1. Laboratory of Drug-Toxicology, Universidade da Beira Interior, Covilhã, Portugal

    Eugenia Gallardo

  2. National Institute of Legal Medicine and Forensic Sciences- South Branch, Lisbon, Portugal

    Mário Barroso

Rights and permissions

Reprints and permissions

Copyright information

© 2022 The Author(s), under exclusive license to Springer Science+Business Media, LLC, part of Springer Nature

About this protocol

Check for updates. Verify currency and authenticity via CrossMark

Cite this protocol

Stefanelli, P., Barbini, D.A. (2022). Advanced and Recent Approaches for Laboratory Methods of Pesticide Residues and Their Metabolites by Mass Spectrometry Techniques. In: Gallardo, E., Barroso, M. (eds) Pesticide Toxicology. Methods in Pharmacology and Toxicology. Humana, New York, NY. https://doi.org/10.1007/978-1-0716-1928-5_1

Download citation

  • DOI: https://doi.org/10.1007/978-1-0716-1928-5_1

  • Published:

  • Publisher Name: Humana, New York, NY

  • Print ISBN: 978-1-0716-1927-8

  • Online ISBN: 978-1-0716-1928-5

  • eBook Packages: Springer Protocols

Publish with us

Policies and ethics

Search

Navigation