Comparison and evaluation of two methods for the pesticide residue analysis of organophosphates in yerba mate

Abstract

Microwave Assisted Extraction and a modified CEN-QuEChERS methodology were evaluated as extraction and clean up procedures for the simultaneous analysis of 42 organophosphate pesticides in yerba mate (Ilex paraguaiensis). The obtained extracts were analyzed by gas chromatography using a flame photometric detector. Linearity, recovery percentages, relative standard deviations, detection and quantification limits and matrix effects were determined according to DG-SANCO guidelines for both methods. At 0.2 and 0.5 mg/kg the evaluated methods showed percentages recoveries between 70 and 120% for most of the analytes. Using Microwave Assisted Extraction methodology, 33 pesticide residues could be properly analyzed whereas only 27 could be determined with the proposed modified QuEChERS. All relative standard deviation were below 18% except for omethoate and disulfoton sulfone when evaluated by the modified QuEChERS. The limits of detection in both methodologies were 0.2 mg/kg for most of the analyzed compounds. The average detection limit for QuEChERS was 0.04 mg/kg. For 19 of the analytes determined through Microwave Assisted Extraction the lowest validated level were 0.004 mg/kg. Signal suppression/enhancement was observed for most of the pesticides, thus matrix-matched calibration curves were used for quantification. The Microwave Assisted Extraction and QuEChERS procedures studied could detect the organophosphate pesticides above the MRL fixed for “mate” by the European Union. They have been successfully applied for the determination of organophosphate pesticide residues in commercial samples and the positives were confirmed through GC–(ITD)-MS.

References

  1. Anastassiades, M., Lehotay, S.J., Štajnbaher, D., Schenck, F.J., 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, 412–431.

    CAS  Article  PubMed  Google Scholar 

  2. Anastassiades, M., Hepperle, J., Roux, D., Sigalov, I., Mack, D., 2010. Extractability of incurred residues using QuEChERS. European Pesticide Residue Workshop. EPRW, Strasbourg, France.

    Google Scholar 

  3. Andrade, F., de Albuquerque, C.A.C., Maraschin, M., da Silva, E.L., 2012. Safety assessment of yerba mate (llex paraquariensis) dried extract: results of acute and 90 days subchronic toxicity studies in rats and rabbits. Food Chem. Toxicol. 50, 328–334.

    Article  PubMed  Google Scholar 

  4. Attallah, E.R., Barakat, D.A., Maatook, G.R., Badawy, H.A., 2012. Validation of a quick and easy (QuEChERS) method for the determination of pesticides residue in dried herbs. J. Food Agric. Environ. 10, 755–762.

    CAS  Google Scholar 

  5. Cajka, T., Sandy, C., Bachanova, V., Drabova, L., Kalachova, K., Pulkrabova, J., Hajslova, J., 2012. Streamlining sample preparation and gas chromatography–tandem mass spectrometry analysis of multiple pesticide residues in tea. Anal. Chim. Acta 743, 51–60.

    CAS  Article  PubMed  Google Scholar 

  6. Cajka, T., Hajslova, J., Lacina, O., Mastovska, K., Lehotay, S.J., 2008. Rapid analysis of multiple pesticide residues in fruit-based baby food using programmed temperature vaporiser injection–low-pressure gas chromatography–high-resolution time-of-flight mass spectrometry. J. Chromatogr. A 1186, 281–294.

    CAS  Article  PubMed  Google Scholar 

  7. Chen, G., Cao, P., Liu, R., 2011. A multi-residue method for fast determination of pesticide in tea by ultra performance liquid chromatography–electrospray tandem mass spectrometry combined with modified QuEChERS sample preparation procedure. Food Chem. 125, 1406–1411.

    CAS  Article  Google Scholar 

  8. Chen, Y., Al-Taher, F., Juskelis, R., Wong, J.W., Zhang, K., Hayward, D.G., Zweigenbaum, J., Stevens, J., Cappozzo, J., 2012. Multiresidue pesticide analysis of dried botanical dietary supplements using an automated dispersive SPE clean up for QuEChERS and high-performance liquid chromatography–tandem mass spectrometry. J. Agric. Food Chem. 60, 9991–9999.

    CAS  Article  PubMed  Google Scholar 

  9. Chen, L., Songa, F., Liua, Z., Zhenga, Z., Xinga, J., Liua, S., 2012. Multi-residue method for fast determination of pesticide residues in plants used in traditional Chinese medicine by ultra-high-performance liquid chromatography coupled to tandem mass spectrometry. J. Chromatogr. A 1225, 132–140.

    CAS  Article  PubMed  Google Scholar 

  10. Cho, S., Abd El-Aty, A.M., Choi, J., Jeong, Y., Shin, H., Chang, B., Lee, C., Shim, J., 2008. Effectiveness of pressurized liquid extraction and solvent extraction for the simultaneous quantification of 14 pesticide residues in Green tea using GC. J. Sep. Sci. 31, 1750–1760.

    CAS  Google Scholar 

  11. European Commission, 2005. Regulation (EC) No. 396/2005 of the European Parliament and of the Council of 23 February 2005 on maximun residue levels of pesticides in or on food and feed of plant and animal origin and amending Council Directive 91/414/EEC. Off. J. Eur. Union, 1–16.

    Google Scholar 

  12. European Commission DG-SANCO, 2014. Method validation and quality control procedures for pesticide residue analysis in food and feed. Document SANCO/12571/2013, 1 January.

    Google Scholar 

  13. EU-MRLs Database. http://ec.europa.eu/sanco pesticides/public/?event=commodity.resultat (accessed June 2014).

  14. Filip, R., Lopez, P., Giberti, G., Coussio, J., Ferraro, G., 2001. Phenolic compounds in seven South American Ilex Species. Fitoterapia 72, 774–778.

    CAS  Article  PubMed  Google Scholar 

  15. Haib, J., Hofer, I., Renaud, J.M., 2003. Analysis of multiple pesticide residues in tobacco using pressurized liquid extraction, automated solid-phase extraction clean up and gas chromatography–tandem mass spectrometry. J. Chromatogr. A 1020, 173–187.

    CAS  Article  PubMed  Google Scholar 

  16. Hayward, D., Wong, J.W., Shi, F., Zhang, K., Lee, N.S., Di Benedetto, L., Hengel, M., 2013. Multiresidue pesticide analysis of botanical dietary supplements using salt-out acetonitrile extraction, solid-phase extraction clean up column, and gas chromatography–triple quadrupole mass spectrometry. Anal. Chem. 85, 4686–4693.

    CAS  Article  PubMed  Google Scholar 

  17. Heck, C.I., de Mejia, E.G., 2007. Yerba mate tea (Ilex paraguariensis): a comprehensive review on chemistry, health, implications, and technological considerations. J. Food Sci. 72, R138–R148.

    CAS  Article  PubMed  Google Scholar 

  18. Huang, Z., Li, Y., Chen, B., Yao, S., 2007. Simultaneous determination of 102 pesticide residues in Chinese teas by gas chromatography–mass spectrometry. J. Chromatogr. B 853, 154–162.

    CAS  Article  Google Scholar 

  19. Huang, Z., Zhang, Y., Wang, L., Ding, L., Wang, M., Yan, H., Li, Y., Zhu, S., 2009. Simultaneous determination of 103 pesticide residues in tea samples by LC–MS/MS. J. Sep. Sci. 32, 1294–1301.

    CAS  Article  PubMed  Google Scholar 

  20. Ingelse, A.B., van Dam, C.J.R., Vreeken, J.R., Mol, G.J.H., 2001. Determination of polar organophosphorus pesticides in aqueous samples by direct injection using liquid chromatography–tandem mass spectrometry. J. Chromatogr. A 918, 67–78.

    CAS  Article  PubMed  Google Scholar 

  21. Jacques, R.A., dos Santos Freitas, L., Flores Peres, V., Dariva, C., Oliveira, J.V., Camarão, E.B., 2006. Chemical composition of mate tea leaves (Ilex paraguariensis): a study of extraction methods. J. Sep. Sci. 29, 2780–2784.

    CAS  Article  Google Scholar 

  22. Jacques, R.A., Santos, J.G., Dariva, C., Oliveira, J.V., Camarão, E.B., 2007. GC/MS characterization of mate tea leaves extracts obtained from high-pressure CO2 extraction. J. Supercrit. Fluids 40, 354–359.

    CAS  Article  Google Scholar 

  23. Kanrar, B., Mandal, S., Bhattacharyya, A., 2010. Validation and uncertainty analysis of a multiresidue method for 42 pesticides in made tea, tea infusion and spent leaves using ethyl acetate extraction and liquid chromatography mass spectrometry. J. Chromatogr. A 1217, 1926–1933.

    CAS  Article  PubMed  Google Scholar 

  24. Lozano, A., Rajski, Ł., Belmonte-Valles, N., Uclés, A., Uclés, S., Mezcua, M., Fernández-Alba, A.R., 2012. Pesticide analysis in teas and chamomile by liquid chromatography and gas chromatography tandem mass spectrometry using a modified QuEChERS method: validation and pilot survey in real samples. J. Chromatogr. A 1268, 109–122.

    CAS  Article  PubMed  Google Scholar 

  25. Khan, Z.S., Ghosh, R.K., Girame, R., Utture, S.C., Gadgil, M., Banerjee, K., Reddy, D.D., Johnson, N., 2014. Optimization of a sample preparation method for multiresidue analysis of pesticides in tobacco by single and multi-dimensional gas chromatography–mass spectrometry. J. Chromatogr. A 1343, 200–206.

    CAS  Article  PubMed  Google Scholar 

  26. Liu, D., Min, S., 2012. Rapid analysis of organochlorine and pyrethroid pesticides in tea samples by directly suspended droplet microextraction using a gas chromatography–electron capture detector. J. Chromatogr. A 1235, 166–173.

    CAS  Article  PubMed  Google Scholar 

  27. Mastovska, K., Lehotay, S.J., 2003. Practical approaches to fast gas chromatography–mass spectrometry. J. Chromatogr. A 1000, 153–180.

    CAS  Article  PubMed  Google Scholar 

  28. Moinfar, S., Hosseini, M.M., 2009. Development of dispersive liquid–liquid microextraction method for the analysis of organophosphorus pesticides in tea. J. Hazard. Mater. 169, 907–911.

    CAS  Article  PubMed  Google Scholar 

  29. Nguyen, T.D., Lee, K.J., Lee, M.H., Lee, G.H., 2010. A multiresidue method for the determination of 234 pesticides in Korean herbs using gas chromatography mass spectrometry. Microchem. J 95, 43–49.

    CAS  Article  Google Scholar 

  30. Niell, S., Pareja, L., González, G., González, J., Vryzas, Z., Cesio, M.V., Papadopoulou-Mourkidou, E., Heinzen, H., 2011. Simple determination of 40 organophosphate pesticides in raw wool using microwave-assisted extraction and GC–FPD analysis. J. Agric. Food Chem. 59, 7601–7608.

    CAS  Article  PubMed  Google Scholar 

  31. Papadakis, E., Vryzas, Z., Papadopoulou-Mourkidou, E., 2006. Rapid method for the determination of 16 organochlorine pesticides in sesame seeds by microwaveassisted extraction and analysis of extracts by gas chromatography–mass spectrometry. J. Chromatogr. A 1127, 6–11.

    CAS  Article  PubMed  Google Scholar 

  32. 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, 1697–1714.

    CAS  Article  PubMed  Google Scholar 

  33. Perez Parada, A., González, J., Pareja, L., Geis Asteggiante, L., Colazzo, M., Niell, S., Besil, N., González, G., Cesio, V., Heinzen, H., 2010. Transfer of pesticides to the brew during mate drinking process and their relationship with physicochemical properties. J. Environ. Sci. Health B 45, 1–8.

    Article  Google Scholar 

  34. Rajski, L., Lozano, A., Belmonte-Valles, N., Uclés, A., Uclés, S., Mezcua, M., Fernandez-Alba, A.R., 2013. Comparison of three multiresidue methods to analyse pesticides in green tea with liquid and gas chromatography/tandem mass spectrometry. Analyst 138, 921–931.

    CAS  Article  PubMed  Google Scholar 

  35. Ravindra, K., Dirtu, A.C., Covaci, A., 2008. Low-pressure gas chromatography: recent trends and developments. Trends Anal. Chem. 27, 291–303.

    CAS  Article  Google Scholar 

  36. Sadowska-Rociek, A., Surma, M., Cieślik, E., 2013. Application of QuEChERS method for simultaneous determination of pesticide residues and PAHs in fresh herbs. Bull. Environ. Contam. Toxicol. 90, 508–513.

    CAS  Article  PubMed  PubMed Central  Google Scholar 

  37. Vazquez, A., Moyna, P., 1986. Studies on mate drinking. J. Ethnopharmacol. 18, 267–272.

    CAS  Article  PubMed  Google Scholar 

  38. Vryzas, Z., Papadakis, E.N., Papadopoulou-Mourkidou, E., 2002. Microwave-assisted extraction (MAE)-acid hydrolysis of dithiocarbamates for trace analysis in tobacco and peaches. J. Agric. Food Chem. 50, 2220–2226.

    CAS  Article  PubMed  Google Scholar 

  39. Vryzas, Z., Papadopoulou-Mourkidou, E., 2002. Determination of triazine and chloroacetanilide herbicides in soils by microwave-assisted extraction (MAE) coupled to gas chromatographic analysis with either GC–NPD or GC–MS. J. Agric. Food Chem. 50, 5026–5033.

    CAS  Article  Google Scholar 

  40. Vryzas, Z., Tsaboula, A., Papadopoulou-Mourkidou, E., 2007. Determination of alachlor, metolachlor, and their acidic metabolites in soils by microwaveassisted extraction (MAE) combined with solid phase extraction (SPE) coupled with GC–MS and HPLC–UV analysis. J. Sep. Sci. 30, 2529–2538, www.cen.eu

    CAS  Article  PubMed  Google Scholar 

  41. Xu, X.M., Yu, C., Han, J.L., Li, J.P., El-Sepai, F., Zhu, Y., Huang, Z.X., Cai, Z.X., Wu, H.W., Ren, Y.P., 2011. Multi-residue analysis of pesticides in tea by online SEC–GC/MS. J. Sep. Sci. 34, 210–216.

    CAS  Article  PubMed  Google Scholar 

Download references

Acknowledgment

The authors gratefully acknowledge the European Commission (Alfa II Programme B-Project EUROLANTRAP, No. AML/B7-311/97/0666/II0461-FA-FCD-FI).

Author information

Affiliations

Authors

Contributions

JG, SN and LP performed the laboratory work, data and chromatographic analysis. HH and ZV ran the first trial experiments with MAE. ZV analyzed the real samples in the GC–(ITD)-MS, LP, ZV and SN drafted the paper. VC, LP and HH gave the works conceptual frame, participated in the results discussion and the manuscript final writing. ZV and EPM supervised the laboratory work and ZV contributed to critical reading of the manuscript.

Corresponding author

Correspondence to Horacio Heinzen.

Ethics declarations

The authors have no conflict of interest to declare.

Rights and permissions

This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons licence, and indicate if changes were made. The images or other third party material in this article are included in the article's Creative Commons licence, unless indicated otherwise in a credit line to the material. If material is not included in the article's Creative Commons licence and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this licence, visit http://creativecommons.org/licenses/by/4.0/.

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Pareja, L., Niell, S., Vryzas, Z. et al. Comparison and evaluation of two methods for the pesticide residue analysis of organophosphates in yerba mate. Rev. Bras. Farmacogn. 25, 98–104 (2015). https://doi.org/10.1016/j.bjp.2015.02.001

Download citation

Keywords

  • Yerba mate
  • Pesticide residues
  • QuEChERS
  • MAE
  • GC–FPD