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A multiresidue method for the analysis of 90 pesticides, 16 PAHs, and 22 PCBs in honey using QuEChERS–SPME

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Abstract

An optimized analytical method was developed for the simultaneous analysis of 90 pesticides, 16 polycyclic aromatic hydrocarbons, and 22 polychlorinated biphenyls. The method was based on quick, easy, cheap, effective, rugged, and safe (QuEChERS) extraction using acetonitrile followed by a dispersive solid-phase extraction cleanup using primary–secondary amine and octadecyl (C18). The extract obtained was concentrated by evaporation and then reconstituted with acetonitrile to prepare it for chromatographic analysis by liquid chromatography–triple-quadrupole tandem mass spectrometry and gas chromatography–ion-trap tandem mass spectrometry, which was preceded by a preconcentration step using solid-phase microextraction with appropriate fibers. The combination of the two extraction steps ensured efficient extract cleanup. The use of the two analytical instruments allowed the analysis of a large number of pollutants with a high reliability rate. The method developed was validated for linearity, which was studied with use of matrix-matched calibration curves in the concentration range between 10 and 3000 ng g−1. The correlation coefficient (R 2) obtained was higher than 0.98 for most of the target compounds, with a relative standard deviation lower than 20% for repeatability and reproducibility. The limits of detection and quantification were lower than 20 and 60 ng g-1 respectively for the compounds analyzed, and the recoveries were between 60% and 103% for most compounds. Finally, the method was tested for its efficiency on real samples by the analysis of three honey samples in which seven pesticides and nine polycyclic aromatic hydrocarbons were determined.

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References

  1. Panseri S, Catalano A, Giorgi A, Arioli F, Procopio A, Britti D, et al. Occurrence of pesticide residues in Italian honey from different areas in relation to its potential contamination sources. Food Control. 2014;38:150–6.

    Article  CAS  Google Scholar 

  2. Panseri S, Manzo A, Chiesa LM, Giorgi A. Melissopalynological and volatile compounds analysis of buckwheat honey from different geographical origins and their role in botanical determination. J Chem. 2013;2013:904202.

    Article  Google Scholar 

  3. Dobrinas S, Birghila S, Coatu V. Assessment of polycyclic aromatic hydrocarbons in honey and propolis produced from various flowering trees and plants in Romania. J Food Comp Anal. 2008;21(1):71–7. doi:10.1016/j.jfca.2007.07.003.

    Article  CAS  Google Scholar 

  4. Raeymaekers B. A prospective biomonitoring campaign with honey bees in a district of Upper-Bavaria (Germany). Environ Monit Assess. 2006;116(1-3):233–43.

    Article  Google Scholar 

  5. Kujawski MW, Namieśnik J. Challenges in preparing honey samples for chromatographic determination of contaminants and trace residues. Trends Anal Chem. 2008;27(9):785–93. doi:10.1016/j.trac.2008.07.004.

    Article  CAS  Google Scholar 

  6. Herrera López S, Lozano A, Sosa A, Hernando MD, Fernández-Alba AR. Screening of pesticide residues in honeybee wax comb by LC-ESI-MS/MS. A pilot study. Chemosphere. 2016;163:44–53. doi:10.1016/j.chemosphere.2016.07.008.

    Article  Google Scholar 

  7. Machado I, Gérez N, Pistón M, Heinzen H, Cesio MV. Determination of pesticide residues in globe artichoke leaves and fruits by GC–MS and LC–MS/MS using the same QuEChERS procedure. Food Chem. 2017;227:227–36. doi:10.1016/j.foodchem.2017.01.025.

    Article  CAS  Google Scholar 

  8. Karami-Mohajeri S, Abdollahi M. Toxic effects of organophosphate, carbamate, and organochlorine pesticides on cellular metabolism of lipids, proteins, and carbohydrates: a comprehensive review. Hum Exp Toxicol. 2011;30(9):1119–40.

    Article  CAS  Google Scholar 

  9. Zheng S, Chen B, Qiu X, Chen M, Ma Z, Yu X. Distribution and risk assessment of 82 pesticides in Jiulong River and estuary in South China. Chemosphere. 2016;144:1177–92.

    Article  CAS  Google Scholar 

  10. Zhou R, Zhu L, Chen Y, Kong Q. Concentrations and characteristics of organochlorine pesticides in aquatic biota from Qiantang River in China. Environ Pollut. 2008;151(1):190–9.

    Article  CAS  Google Scholar 

  11. de Lima RF, Dionello RG, Peralba MCR, Barrionuevo S, Radunz LL. Reichert Júnior FW. PAHs in corn grains submitted to drying with firewood. Food Chem. 2017;215:165–70. doi:10.1016/j.foodchem.2016.07.164.

    Article  Google Scholar 

  12. Fiandanese N, Borromeo V, Berrini A, Fischer B, Schaedlich K, Schmidt J-S, et al. Maternal exposure to a mixture of di(2-ethylhexyl) phthalate (DEHP) and polychlorinated biphenyls (PCBs) causes reproductive dysfunction in adult male mouse offspring. Reprod Toxicol. 2016;65:123–32. doi:10.1016/j.reprotox.2016.07.004.

    Article  CAS  Google Scholar 

  13. Abdel-Shafy HI, Mansour MSM. A review on polycyclic aromatic hydrocarbons: source, environmental impact, effect on human health and remediation. Egypt J Petroleum. 2016;25(1):107–23.

    Article  Google Scholar 

  14. Elorduy I, Elcoroaristizabal S, Durana N, García J, Alonso L. Diurnal variation of particle-bound PAHs in an urban area of Spain using TD-GC/MS: influence of meteorological parameters and emission sources. Atmos Environ. 2016;138:87–98.

    Article  CAS  Google Scholar 

  15. Kodavanti PRS. Polychlorinated biphenyls (PCBs)☆. In: Reference module in neuroscience and biobehavioral psychology. Elsevier; 2017. doi:10.1016/B978-0-12-809324-5.03955-9.

  16. Amendola G, Pelosi P, Dommarco R. Solid-phase extraction for multi-residue analysis of pesticides in honey. J Environ Sci Health B. 2010;46(1):24–34.

    Article  Google Scholar 

  17. Kujawski MW, Namieśnik J. Levels of 13 multi-class pesticide residues in Polish honeys determined by LC-ESI-MS/MS. Food Control. 2011;22(6):914–9.

    Article  CAS  Google Scholar 

  18. Rissato SR, Galhiane MS, Knoll FR, Apon BM. Supercritical fluid extraction for pesticide multiresidue analysis in honey: determination by gas chromatography with electron-capture and mass spectrometry detection. J Chromatogr A. 2004;1048(2):153–9.

    Article  CAS  Google Scholar 

  19. Sanchez-Brunete C, Albero B, Miguel E, Tadeo JL. Determination of insecticides in honey by matrix solid-phase dispersion and gas chromatography with nitrogen–phosphorus detection and mass spectrometric confirmation. J AOAC Int. 2002;85(1):128–33.

    CAS  Google Scholar 

  20. Chiesa LM, Labella GF, Giorgi A, Panseri S, Pavlovic R, Bonacci S, et al. The occurrence of pesticides and persistent organic pollutants in Italian organic honeys from different productive areas in relation to potential environmental pollution. Chemosphere. 2016;154:482–90. doi:10.1016/j.chemosphere.2016.04.004.

    Article  CAS  Google Scholar 

  21. Anastassiades M, Lehotay SJ, Štajnbaher D, Schenck FJ. 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. 2003;86(2):412–31.

    CAS  Google Scholar 

  22. Albinet A, Tomaz S, Lestremau F. A really quick easy cheap effective rugged and safe (QuEChERS) extraction procedure for the analysis of particle-bound PAHs in ambient air and emission samples. Sci Total Environ. 2013;450:31–8.

    Article  Google Scholar 

  23. Wilkowska A, Biziuk M. Determination of pesticide residues in food matrices using the QuEChERS methodology. Food Chem. 2011;125(3):803–12.

    Article  CAS  Google Scholar 

  24. Arthur CL, Pawliszyn J. Solid phase microextraction with thermal desorption using fused silica optical fibers. Anal Chem. 1990;62(19):2145–8.

    Article  CAS  Google Scholar 

  25. Li J, Wang Y-B, Li K-Y, Cao Y-Q, Wu S, Wu L. Advances in different configurations of solid-phase microextraction and their applications in food and environmental analysis. Trends Anal Chem. 2015;72:141–52. doi:10.1016/j.trac.2015.04.023.

    Article  CAS  Google Scholar 

  26. Bojko B, Pawliszyn J. In vivo and ex vivo SPME: a low invasive sampling and sample preparation tool in clinical bioanalysis. Bioanalysis. 2014;6(9):1227–39.

    Article  CAS  Google Scholar 

  27. Megson D, Reiner EJ, Jobst KJ, Dorman FL, Robson M, Focant J-F. A review of the determination of persistent organic pollutants for environmental forensics investigations. Anal Chim Acta. 2016. doi:10.1016/j.aca.2016.08.027.

    Google Scholar 

  28. García-Valcárcel AI, Molero E, Tadeo JL, Hernando MD. Determination of selected environmental contaminants in foraging honeybees. Talanta. 2016;148:1–6. doi:10.1016/j.talanta.2015.10.064.

    Article  Google Scholar 

  29. Díez C, Traag WA, Zommer P, Marinero P, Atienza J. Comparison of an acetonitrile extraction/partitioning and “dispersive solid-phase extraction” method with classical multi-residue methods for the extraction of herbicide residues in barley samples. J Chromatogr A. 2006;1131(1–2):11–23. doi:10.1016/j.chroma.2006.07.046.

    Article  Google Scholar 

  30. Wiest L, Buleté A, Giroud B, Fratta C, Amic S, Lambert O, et al. Multi-residue analysis of 80 environmental contaminants in honeys, honeybees and pollens by one extraction procedure followed by liquid and gas chromatography coupled with mass spectrometric detection. J Chromatogr A. 2011;1218(34):5743–56.

    Article  CAS  Google Scholar 

  31. Ouyang G, Jiang R (eds) (2016) Solid phase microextraction: recent developments and applications. Springer, Berlin

  32. Walorczyk S, Gnusowski B. Development and validation of a multi-residue method for the determination of pesticides in honeybees using acetonitrile-based extraction and gas chromatography–tandem quadrupole mass spectrometry. J Chromatogr A. 2009;1216(37):6522–31.

    Article  CAS  Google Scholar 

  33. Shabir GA. Validation of high-performance liquid chromatography methods for pharmaceutical analysis: Understanding the differences and similarities between validation requirements of the US Food and Drug Administration, the US Pharmacopeia and the International Conference on Harmonization. J Chromatogr A. 2003;987(1–2):57–66. doi:10.1016/S0021-9673(02)01536-4.

    Article  CAS  Google Scholar 

  34. Malhat FM, Haggag MN, Loutfy NM, Osman MA, Ahmed MT. Residues of organochlorine and synthetic pyrethroid pesticides in honey, an indicator of ambient environment, a pilot study. Chemosphere. 2015;120:457–61.

    Article  CAS  Google Scholar 

  35. Moniruzzaman M, Rodríguez I, Ramil M, Cela R, Sulaiman SA, Gan SH. Assessment of gas chromatography time-of-flight accurate mass spectrometry for identification of volatile and semi-volatile compounds in honey. Talanta. 2014;129:505–15. doi:10.1016/j.talanta.2014.06.019.

    Article  CAS  Google Scholar 

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Acknowledgements

We gratefully acknowledge AZM & SAADE Association and the Lebanese University for funding the project, as well as Strasbourg University for international mobility aid, without which the present study could not have been completed.

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Authors and Affiliations

  1. Laboratory of Applied Biotechnology, Azm Center for Research in Biotechnology and Its Applications, Doctoral School of Science and Technology, Lebanese University, El Mittein Street, 1300, Tripoli, Lebanon

    Josephine Al-Alam, Ziad Fajloun & Asma Chbani

  2. Institute of Chemistry and Processes for Energy, Environment and Health ICPEES UMR 7515 Group of Physical Chemistry of the Atmosphere, University of Strasbourg, 1, rue Blessig, 67084, Strasbourg, France

    Josephine Al-Alam & Maurice Millet

  3. Faculty of Sciences III, Lebanese University, 1300, Tripoli, Lebanon

    Ziad Fajloun

  4. Faculty of Public Health III, Lebanese University, 1300, Tripoli, Lebanon

    Asma Chbani

Authors
  1. Josephine Al-Alam
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  2. Ziad Fajloun
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  4. Maurice Millet
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Correspondence to Maurice Millet.

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Al-Alam, J., Fajloun, Z., Chbani, A. et al. A multiresidue method for the analysis of 90 pesticides, 16 PAHs, and 22 PCBs in honey using QuEChERS–SPME. Anal Bioanal Chem 409, 5157–5169 (2017). https://doi.org/10.1007/s00216-017-0463-y

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  • DOI: https://doi.org/10.1007/s00216-017-0463-y

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